WO2006051840A1 - Colorant dispersion liquid, colored resin composition, color filter and liquid crystal display - Google Patents

Abstract

Disclosed is a colorant dispersion liquid which enables to reduce the amount of undissolved photosensitive colored composition remaining in non-image portions on a substrate when it is applied over the substrate. The colorant dispersion liquid has excellent adhesion to the substrate and does not deteriorate image-forming properties such as curability, so that it enables to produce a color filter having high concentration and low film thickness. In addition, since drying/clogging at a die lip edge is suppressed during application of this colorant dispersion liquid by die coating, this colorant dispersion liquid enables to produce a color filter with high yield. Specifically disclosed is a colorant dispersion liquid containing a colorant (A), a dispersing agent (B) and a solvent (C) which is characterized in that the dispersing agent (B) contains at least a graft copolymer (a) containing a nitrogen atom and a polymer (b) which is obtained by polymerizing a monomer component essentially containing a specific compound.

Description

 Specification

 Color material dispersion, colored resin composition, color filter, and liquid crystal display

 The present invention relates to a color material dispersion, a colored resin composition (hereinafter sometimes referred to as “resist”), a color filter, and a liquid crystal display device. Specifically, high-density and low-thickness pixels can be formed uniformly, have high pattern adhesion during development with little remaining in the non-image area after development, and at the tip of the die lip when applied by die coating. A coloring material dispersion in which the generation of dry aggregates is suppressed, a colored resin composition using the coloring material dispersion, a color filter in which pixels are formed using the coloring resin composition, and this color filter The present invention relates to a liquid crystal display device provided.

 Background art

 Conventionally, pigment dispersion methods, dyeing methods, electrodeposition methods, and printing methods are known as methods for producing color filters used in liquid crystal display devices and the like. Among them, the pigment dispersion method having excellent characteristics on average is most widely adopted from the viewpoints of spectral characteristics, durability, pattern shape and accuracy.

In recent years, the trend of technological innovation has been rapid, and higher transmission and higher density have been required for color filters. In order to form a high-concentration color filter, it was necessary to increase the color material concentration in the colored resin composition to be used. On the other hand, components that contribute to image forming properties such as photosensitivity, solubility, and curability are relatively reduced, and the original image forming performance is lost. That is, for example, when attempting to reduce the pixel thickness by increasing the density (thinning the film thickness), the curability is lowered, the surface smoothness of the pixel is lowered, and the liquid crystal is poorly aligned. Further, when the solubility is lowered, the undissolved product of the colored resin composition in the non-image area after development tends to remain. Further, when the undissolved colored resin composition remains on the non-pixel portion on the substrate, the resulting color filter may cause a decrease in transmittance or contrast. As a result, there was a situation that affected the subsequent process, such as peeling of the film and deterioration of the sealing performance in the liquid crystal cell process. [0003] In order to solve these problems, an attempt has been made to maintain image forming property while maintaining a high colorant concentration by using a dispersant having both a dispersing function and a binder function (Patent Document 1). 2).

 On the other hand, various new technologies have also been developed for color filter manufacturing methods. Among the pixel forming processes, for example, with respect to the resist coating process, it has been the mainstream to apply a resist to the center of the substrate and make it uniform by spin coating. However, as the size of the substrate increases, the amount of resist used increases, and the restrictions on the spin coater equipment (such as the motor capability) are large. A coating technique based on the die coating method has been developed and is in practical use.

 Patent Document 1: JP 2001-108817

 Patent Document 2: Japanese Patent Application Laid-Open No. 2004-46047

 Disclosure of the invention

 Problems to be solved by the invention

However, the dispersant having both the dispersing function and the binder function has the following problems. That is,

 (i) A dispersant having both a dispersing function and a binder function, particularly in a resist having a high colorant concentration, is less effective in each of the dispersing function and the binder function than a conventional combination of a dispersing agent and a binder resin. It was enough.

 (ii) For this reason, the conventional dispersant and binder resin were eventually used together, and the proportion of the above components in the color material dispersion and the colored resin composition increased.

 This has been a factor that makes it difficult to increase the colorant density.

 (iii) When a dispersant having both a dispersing function and a binder function and a binder resin are used in combination, performance such as developability, solubility and curability may be deteriorated.

[0005] Further, as a technique for applying a resist by a die coating method, in the case of single wafer coating such as a color filter, the coating method is intermittent coating, and the tip of the die lip is repeatedly wetted and dried. When a color resist or black resist in which a high concentration of pigment is dispersed is dried at the tip of the die, the pigment concentration increases rapidly, and agglomeration of the pigment may occur. These agglomerates adhere to the tip of the die lip and become rit when the resist is discharged again. It peels off from the tip of the wafer and moves onto the substrate, but it is not easily removed in the subsequent processes and remains on the substrate until the end. Such an agglomerate becomes a pixel defect of the color filter and causes a quality defect. If this defect occurs frequently, the yield of the product will decrease, which is one of the phenomena that must be avoided. For this reason, there were cases in which the generation of foreign matter due to dry aggregation at the tip of the die lip could not be sufficiently suppressed during coating by the die coating method.

 [0006] The present invention has been made in view of the above-mentioned problems, and its object is as follows.

 (1) When applied on a substrate, the undissolved colored resin composition is hardly left in the non-image area on the substrate. It is possible to produce a color filter with a high concentration and a low film thickness that can be reduced, and a colorant dispersion that can produce a color filter at a high yield by suppressing dry aggregation at the tip of the die lip when applied by die coating. To provide.

 (2) When coated on a substrate, the undissolved colored resin composition is hardly left in the non-image area on the substrate. A colored resin composition capable of producing a color filter having a high concentration and a low film thickness that can be reduced without reducing the drying and aggregation at the tip of the die lip and capable of producing a color filter at a high yield when applied by die coating. To provide.

 (3) A high-quality color filter with a high density and a low film thickness, in which no undissolved colored resin composition or foreign matter resulting from drying and agglomeration during die coating remains on the non-pixel area on the substrate. To provide.

 (4) To provide a high-quality liquid crystal display device using the color filter substrate described in (3) above.

 Means for solving the problem

[0007] As a result of intensive investigations to solve the above problems, the present inventors have obtained a stable colorant dispersion with a small amount of dispersant added to the colorant by combining a dispersant having a specific structure. By using this dispersion, it has excellent adhesion to the substrate without undissolved matter remaining in the non-image area on the substrate without deteriorating the image forming ability such as curability and high concentration. Color pixels can be formed uniformly, and the tip of the die lip is applied during die coating. The present inventors have found that a colored resin composition in which the generation of dry agglomerates at the ends can be suppressed can be achieved.

 The present invention comprises a plurality of related inventions, and the gist of each invention is as follows.

(1) (A) a color material, (B) a dispersant, and (C) a color material dispersion containing a solvent, wherein (B) the dispersant contains at least (a) a graft copolymer containing a nitrogen atom, and Z or an acrylic block copolymer, and (b) a polymer obtained by polymerizing a monomer component essentially comprising a compound represented by the following general formula (1) and / or (2) Color material dispersion.

[Chemical 1]

(In formula (1), R ^la and R ^2a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)

[Chemical 2]

(In the formula (2), R ^lb represents a hydrogen atom or an alkyl group which may have a substituent, and L ³ represents A divalent linking group or a direct bond is represented, and X represents a group represented by the following formula (3) or an adamantyl group which may be substituted. )

 [Chemical 3]

L²及び L³の 2以上が互いに結合 し、環を形成していてもよい。 ) (In Formula (3), R ^2b , R ^3b , and R ^4b represent a hydrogen atom, a hydroxyl group, a halogen atom, an amino group, or an organic group, L ¹ and L ² represent a divalent linking group,

Two or more of L ² and L ³ may be bonded to each other to form a ring. )

[0009] (2) A colored resin composition containing (A) a colorant, (B) a dispersant, and (C) a solvent, wherein (B) the dispersant contains at least (a) a nitrogen atom. Polymer and Z or acrylic block copolymer, and (b)) a polymer obtained by polymerizing a monomer component essentially comprising the compound represented by the general formula (1) and Z or (2). Colored resin composition characterized in that

(3) A color finer formed using the colored resin composition according to (2).

 (4) A liquid crystal display device formed using the color filter according to (3).

 The invention's effect

[0010] The present invention has the following effects.

(1) According to the colorant dispersion of the present invention, when applied onto a substrate, the undissolved colored resin composition is less likely to remain in the non-image area on the substrate, and the adhesion to the substrate is reduced. It produces a color filter with a high density and a low film thickness that does not degrade the image-forming ability such as the hardenability. In addition, when applying by die coating, drying aggregation at the tip of the die lip can be suppressed, and a color filter can be produced with a high yield.

 (2) According to the colored resin composition of the present invention, when applied onto the substrate, the undissolved matter of the colored resin composition is less likely to remain in the non-image area on the substrate, thereby improving adhesion to the substrate. In addition, it is possible to manufacture color filters with high density and low film thickness that do not reduce image forming ability such as curability, and at the time of application by die coating, drying agglomeration at the tip of the die lip is suppressed, resulting in high yield. Color filters can be manufactured.

 (3) The color filter of the present invention has a high concentration and a low film thickness with no undissolved colored resin composition or foreign matter resulting from dry aggregation during die coating applied to the non-pixel portion on the substrate. High quality.

 (4) The liquid crystal display device of the present invention is of high quality because it uses the high quality color filter described in (3) above.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0011] The constituent requirements of the present invention will be described in detail below, but these are examples of embodiments of the present invention, and the present invention is not limited to these contents.

 [1] Components of colorant dispersion

 Hereinafter, each component of the color material dispersion of the present invention will be described. The color material dispersion of the present invention comprises a color material, a dispersant, and a solvent as essential components, and if necessary, may contain other additives other than the above components. Hereinafter, each component will be described.

 [0012] It should be noted that Γ (meth) acryl ", Γ (meth) acrylate" and the like mean "acryl and / or methacryl", "attalate and / or metatalylate" and the like, for example, "(meth) Acrylic acid

"Means" acrylic acid and Z or methacrylic acid ". In the section [1], “total solids” refers to all components of the colorant dispersion of the present invention other than the solvent components described later.

 [0013] [1 1] (A) Color material

(A) The color material means a color material for the color material dispersion of the present invention. Dye pigments can be used as the color material, but point pigments such as heat resistance and light resistance are preferred. Blue, green, red, yellow, purple, orange, brown, and black pigments Various color pigments can be used. In addition to the organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments are also included. It is available. Specific examples of pigments that can be used are shown below by pigment numbers. The following “CI” means the color index (CI).

[0014] CI pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37 , 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53 : 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81 : 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144 , 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 20 0, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247 , 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 26 7, 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, preferably ί or CI pigment red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably ί or CI pigment red 177, 209, 224, The ability to raise 254 S.

 [0015] Blue pigments include C. I. Pigment Benore 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15:

 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Among these, C.I. pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. pigment blue 15: 6 can be mentioned.

 [0016] CI pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18 8, 19, 26, 36, 45, 48, 50, 51, 54, You can raise 55 and have the power S. Among these, CI Pigment Green 7 and 36 are preferable.

CI pigment yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13 , 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154

 , 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 16 9, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 1 89, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 20 2, 203, 204, 205, 206, 207, 208 You can list it. Among these, preferably CI pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably CI pigment yellow 83, 138, 139, 150, 180 it can.

 [0017] The CI range pigment range is 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48. 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among these, C.I. Pigment Orange 38 and 71 are preferable.

 [0018] Purple pigments include CI pigment violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Among these, C.I. pigment violet 19, 23 is preferable, and C.I. pigment violet 23 is more preferable.

 [0019] When the color material dispersion of the present invention is a color material dispersion for a black matrix of a color filter, a black color material can be used as the color material. The black color material may be a black color material alone or a mixture of red, green, blue, etc. These coloring materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, it is preferable to use the pigment dispersed in an average particle size of 1 z m or less, preferably 0.5 z m or less.

[0020] Color materials that can be mixed to prepare a black color material include Victoria Pure Blue (42595), Auramin 0 (41000), Catillon Brilliant Flavin (Basic 13), Rho Damin 6GCP (45160), Rhodamine B (45170), Safranin OK70: 100 (50240), Elizabeth Ku, 'Lausin X (42080), No.120 / Li Nore Yellow (21090), Li Nonolayero GRO (21090), Shimla First Yellow 8GF (21105), Benzine Yellow 4T—564D (21095), Shimla First Red 4015 (12355), Re-born Norre Red 7B 4401 (15850), Fast Gen Blue TGR— L (74160), Lionol Blue SM (2 6150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. The number in the figure means the color index (CI)).

 [0021] Further, other pigments that can be used in combination are represented by CI numbers. For example, CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 1 53, 154, 166, CI orange pigment 36, 43, 51, 55, 59, 61, CI red pigment 9, 9 7, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 2 26, 227, 228, 240, CI violet pigment 19, 23, 29, 30, 37, 40, 50, CI blue pigment 15, 15: 1, 15: 4, 22, 60 64, CI green pigment 7, CI brown pigment 23, 25, 26 and the like.

 [0022] Examples of black color materials that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, vanillin black, cyanine black, and titanium black.

 Among these, carbon black and titanium black are preferable from the viewpoints of light shielding ratio and image characteristics. Examples of carbon black include the following carbon black. Made by Mitsubishi Gakaku: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 4 7, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 31 50, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, 〇IL7B, OIL9B, OIL11B, OIL30B, OIL31

Made by Degussa: Printex3, Printex30P, Printex30, Printex30OP, Printex40, Priirex45, Priirex55, Priirex60, Priirex75, Printex80, Printex85, Prin tex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V , Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

Made by Cabot: Monarchl20, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, MonarchlOOO, Monarchl 100, Monarchl300, Monarchl400, Monarch4630, REGAL99R, REGAL415, RE GAL415R, REGAL250, REGR250, REGR330, REGR330, REGAL330, REGAL330 BLACK PEARLS480, PEARLS 130, VULCAN

XC72R, ELFTEX-8

Made by Colombian Carbon: RAVEN11, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RA VEN1000, RAVEN 1020, RAVEN 1040U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN 1250, RAVEN 1500, RAVEN200 00, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN 5750, RAVEN7000

 Examples of titanium black include the following.

Titanium black can be produced by heating and reducing a mixture of titanium dioxide and metallic titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), or by high-temperature hydrolysis of tetrasalt titanium. A method of reducing ultrafine titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069). And a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610). It is not limited to these. [0024] Examples of commercially available titanium black products include Titanium Black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials.

 As examples of other black pigments, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments.

 In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, and the like can be used as the pigment.

 [0025] A plurality of the above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

 The average particle size of these pigments is usually 1 μm, preferably 0.5 μm or less, and more preferably 0.25 × m or less. Examples of the dye that can be used as the coloring material include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinonimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

 [0026] Examples of azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Benolet 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12 , CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Day Sparse Orange 5, CI Day Examples include Spar Thread 58, CI Day Spurs Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, CI Mordant Black 7.

 [0027] Examples of anthraquinone dyes include CI Bat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Benolet 19, CI Reactive Benore 49, CI Disperse Red 60, CI Disperse Blue 56, CI parse blue 60, etc.

In addition, phthalocyanine dyes such as CI pad blue 5 isotropic quinone imine dyes such as CI basic blue 3 and CI basic blue 9 Examples of quinoline dyes include CI Solvent Yellow 33, CI Acid Yellow 3, CI Disperse Yellow 64, and nitro dyes such as CI Acid Yellow 1, CI Acid Orange 3, CI Disperse Yellow 42, etc. Can be mentioned.

 [0028] The ratio of the color material to the total solid content in the color material dispersion of the present invention is usually 10 to 90% by weight, preferably 30 to 90% by weight, and more preferably 50 to 90% by weight. If the content ratio of the coloring material is too small, the coloring power is lowered, and the film thickness becomes too thick with respect to the color density, which adversely affects the gap control during liquid crystal cell formation. On the other hand, if the content ratio of the coloring material is too large, the dispersion stability deteriorates, and there is a risk of problems such as re-aggregation and thickening.

 [0029] [1 1 2] (B) Dispersant

 The colorant dispersion of the present invention comprises (B) a dispersant containing at least (a) a draft copolymer containing nitrogen atoms and Z or an acrylic block copolymer, and (b) a specific compound as a dispersant. It is essential to include a polymer obtained by polymerizing monomer components. Hereinafter, each dispersant will be described in detail.

 [0030] [1 2-1] Graft copolymer containing nitrogen atom

 The graft copolymer containing a nitrogen atom as the component (a) preferably has a repeating unit containing a nitrogen atom in the main chain. Among them, it is preferable to have a repeating unit represented by the formula (I) or / and a repeating unit represented by the formula (II).

 [0031] [Chemical 4]

(In the formula, R represents an alkylene group having 1 to 5 carbon atoms, A represents a hydrogen atom or the following formulas (III) to (

 1

 V) represents one of the following. )

 In the above formula (I), R is a linear or branched carbon such as methylene, ethylene or propylene.

 1

Represents an alkylene group having 1 to 5 prime atoms, preferably 2 to 3 carbon atoms, and more preferably an ethylene group. A is a hydrogen atom or a force representing any one of the following formulas (ΠΙ) to (ν), preferably Formula (III). [0033] [Chemical 5]

,

In the above formula (Π), R and A are synonymous with R and A in formula (I) _c

 1 1

 [0035] [Chemical 6] H o AI

[0036] In the above formula (ΠΙ), W represents a linear or branched group having 2 to 10 carbon atoms,

 1

 Of these, a group having 4 carbon atoms such as butylene, pentylene and hexylene is preferred. ρ represents an integer of 1 to 20, preferably an integer of 5 to 10

[0037] [Chemical 7]

[0038] In the above formula (IV), Υ represents a divalent linking group, in particular, the number of carbons such as ethylene and propylene.

 1

 An alkylene group having 1 to 4 carbon atoms and an alkyleneoxy group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy are preferable. W is linear or branched such as ethylene, propylene, butylene

 2

This represents a branched alkylene group having 2 to 10 carbon atoms, and an alkylene group having 2 to 3 carbon atoms such as ethylene and propylene is particularly preferable. Υ is a hydrogen atom or one CO—R (R is ethyl, Represents an alkyl group having 1 to 10 carbon atoms such as pill, butyl, pentyl and hexyl, and an alkyl group having 2 to 5 carbon atoms such as ethyl, propyl, butyl and pentyl is particularly preferable. q represents an integer of 1 to 20, preferably an integer of 5 to 10;

 [0039] [Chemical 8]

 [0040] In the above formula (V), W is a carbon having 1 to 5 carbon atoms and an alkyl group or a hydroxyl group having 1 to 5 carbon atoms.

 Three

 It represents a hydroxyalkyl group having 1 to 50 carbon atoms. Among them, an alkyl group having 10 to 20 carbon atoms such as stearyl and a hydroxyalkyl group having 10 to 20 carbon atoms having 1 to 2 hydroxyl groups such as monohydroxystearyl are preferable.

 The content of the repeating unit represented by the formula (I) or (表) in the graft copolymer of the present invention is usually higher than 50 mol%, preferably higher than 70 mol%. There is no particular limitation on the content ratio of the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II). It contains more repeating units and is preferred. The total number of repeating units represented by formula (I) or formula (Π) is usually:! -100, preferably 10-70, more preferably 20-50. Further, examples of other repeating units that may contain repeating units other than those represented by formula (I) and formula (Π) include an alkylene group and an alkyleneoxy group. The graft copolymer of the present invention preferably has a terminal of —NH and —R—NH (R is as defined above for R).

 2 1 2 1 1

 [0041] In the graft copolymer of the present invention, the main chain may be linear or branched.

The amine value of the graft copolymer of the present invention is usually 5 to: 100 mgKH / g, preferably 10 to 70 mgKH / g, more preferably 15 to 40 mgKH / g or less. is there. If the amine value is too low, the dispersion stability may decrease and the viscosity may become unstable. Conversely, if the amine value is too high, the residue may increase or the electrical characteristics after the liquid crystal panel is formed may deteriorate. The

 [0042] The weight average molecular weight of the above dispersant measured by GPC is preferably from 3000 to 100000 force S, preferably from 5000 to 50000 force S. If the weight average molecular weight is less than 3000, aggregation of the coloring material cannot be prevented and the viscosity or gelation may occur. If the weight average molecular weight exceeds 100000, the viscosity itself becomes high, and it dissolves in an organic solvent. It is not preferable because of lack of sex.

 [0043] As a method for synthesizing the dispersant, a known method can be adopted, and for example, a method described in Japanese Patent Publication No. 63-30057 can be used.

 In the present invention, a commercially available graft copolymer having the same structure as described above can be applied.

[0044] [1 1-2-2] Acrylic block copolymer

 As the acrylic block copolymer of component (a), the A block having a quaternary ammonium base and / or amino group in the side chain, the B block having a quaternary ammonium base and / or amino group, Preferred are A-B block copolymers and / or B-A-B block copolymers.

 [0045] The A block constituting the block copolymer of the acrylic block copolymer has a quaternary ammonium base and / or an amino group.

The quaternary ammonium base is preferably —N ⁺ RRR · Υ— (where R 1, R 2 and R are

 la 2a 3a la 2a m Each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, two or more of R 1, R 2 and R are bonded together to form a cyclic structure

 la 2a 3a

 You may do it. Y— represents an anion. It has a quaternary ammonium base represented by This quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

[0046] In -N ⁺ RRR, two or more of R 1, R 2 and R 3 are bonded to each other.

 la 2a 3a la 2a 3a

 Examples of the cyclic structure include a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring obtained by condensing two of these. The nitrogen-containing heterocycle is more preferably a saturated ring that is preferably non-aromatic. Specific examples include the following.

[0047] [Chemical 9]

 [0048] (In the above formula, R represents any group of R 1 to R 4)

 la 3a

 These cyclic structures may further have a substituent.

-R ⁺ R in N ⁺ RRR may be more preferably la 2a 3a la 3a

 It is an alkyl group having 1 to 3 carbon atoms, a phenyl group which may have a substituent, or a substituent having a substituent, which may be a benzyl group.

[0049] The A block is particularly preferably one containing a partial structure represented by the following general formula (VI).

[0050] [Chemical 10]

(In the general formula (VI), R ^ld , R ^2d , and R ^3d each independently represent a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, R ^ld Two or more of R ^2d and R ^3d may be bonded to each other to form a cyclic structure, R ^4d represents a hydrogen atom or a methyl group, X represents a divalent linking group, Y— represents an anion.)

In the general formula (VI), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, one CONH—R ^5d —, one COO R ^6d — (provided that R ^5d and R ^6d are a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (one R ^7d _ 0 _R ^8d —: R ^7d and R ^8d are each independently Represents an alkylene group), and the like. COO—R ^M — is preferable.

[0052] Examples of Y- for anions include Cl-, Br-, Γ, CIO-, BF-, CH COO-, and PF-.

The amino group is preferably —NR ^le R ^2e (where R ^le and R ^2e are each independently a cyclic or chain-like alkyl group which may have a substituent, or a substituent. It represents a good aryl group or an aralkyl group which may have a substituent, and more preferably an amino group represented by the following formula.

[0053] [Chemical 11]

[0054] (wherein, R ^le and R ^2e, the above R ^le and R ^2e synonymous, R ^3e represents an alkylene group, R ^4e represents a hydrogen atom or a methyl group having at least one carbon atom.)

Of these, R ^le and R ^2e are preferably methyl groups, R is preferably a methylene group, and ethylene groups are preferred. R ^4e is preferably a hydrogen atom. Examples of such a compound include a substituent represented by the following formula.

[0055] [Chemical 12]

[0056] The partial structure containing the specific quaternary ammonium base and / or amino group as described above may be contained in two or more kinds in one A block. In that case, two or more kinds of quaternary ammonium base and / or amino group-containing partial structure may be contained in the A block in any form of random copolymerization or block copolymerization. Examples of the partial structure that may be contained in the partial structural force S, A block that does not contain the quaternary ammonium base and / or amino group include (meth) acrylic acid ester monomers described below. Examples include a partial structure derived from the origin. Powerful quaternary ammonium base and / or a partial structure containing no amino group in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably, the ammonium base and / or amino group-free partial structure is not included in the A block.

[0057] On the other hand, as the B block constituting the block copolymer of the dispersant, for example, styrene monomers such as styrene and a-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (meta) ) Propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2 _ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate , Hydroxyethyl (meth) ate, (Meth) acrylic acid ester monomers such as glycidyl thiolate and N, N-dimethylaminoethyl (meth) acrylate; (meth) acrylate monomers such as (meth) acrylic chloride; (meth) acrylamide, (Meth) acrylamide monomers such as N-methylolacrylamide, N, N-dimethylacrylamide, N, N-dimethylaminoethylacrylamide; butyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate etherol; N-methacryloylmorpholine, A polymer structure obtained by copolymerizing comonomers such as

 [0058] The B block is particularly preferably a partial structure derived from a (meth) acrylic acid ester monomer represented by the following general formula (VII).

[0059] [Chemical 13]

(In the above general formula (VII), R ^9d represents a hydrogen atom or a methyl group. R ^1W has a cyclic or chain alkyl group which may have a substituent, or a substituent. Represents an aryl group that may be substituted, or an aralkyl group that may have a substituent.

 Two or more types of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block. Of course, the B block may further contain a partial structure other than these. Partial structural strength derived from two or more monomers No quaternary ammonium salt group When present in the B block, each partial structure is contained in the B block in any form of random copolymerization or block copolymerization. May be. When the B block contains a partial structure other than the partial structure derived from the (meth) acrylic acid ester monomer, the content of the partial structure other than the (meth) acrylic acid ester monomer in the B block Is preferably 0 to 99% by weight, more preferably 0 to 85% by weight.

[0061] The acrylic dispersant used in the present invention comprises such an A block and a B block. One B block or B—A—B block copolymer type polymer compound. Such a block copolymer is prepared, for example, by the living polymerization method shown below.

 The living polymerization method includes an anion living polymerization method, a cationic living polymerization method, and a radical living polymerization method. In the anion living polymerization method, the polymerization active species is anion, for example, shown in the following scheme.

[Chemical 14]

(Anion living polymerization method)

Combination of

[0063] ラジカルリビング重合法は重合活性種がラジカルであり、例えば下記スキームで示 される。

[0063] In the radical living polymerization method, the polymerization active species is a radical, and is represented by the following scheme, for example.

[0064] [Chemical 15]

(Radical living polymerization method: dixyl method) Mono

Mono

[0065] [Chemical 16] (Radical living polymerization method: ATRP¾) Mono-mono (2): H _? C— CH

COOR ^fi

Me:遷移金属

Me: Transition metal

Monomer -¾

Mono 7_

[0066] In synthesizing such an acrylic block copolymer, JP-A-60-89452, JP-A-9 62002, P. Lutz, P. Masson et al, Polym. Bull. 12 , 79 (1984), BC Anderson, GD Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986) ), Hiroshi Right-hand, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 46, 18 9 (1989), M. Kuroki, T. Aida, J Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al, Macro molecules, 20, 1473 (1987), , K. Matyaszewski et al, Chem. Rev. 2001, 101, 2921-2990, etc. can be employed.

[0067] In the A-B block copolymer and B-A-B block copolymer lg according to the present invention, 4 If the amount of the class ammonium base is preferably 0.1 to:! Ommol, outside this range, it may not be possible to combine good heat resistance and dispersibility.

 Such a block copolymer usually contains an amino group generated in the production process. Its amine value is about 1 to:! OOmg-KOH / g. The amine value is a value expressed in mg of KOH corresponding to the acid value after neutralization titration of the basic amino group with an acid.

 [0068] In addition, the acid value of this block copolymer is a force depending on the presence and type of acidic group that is the basis of the acid value, and generally it is preferably lower than lOOmg-KOHZg, and its molecular weight The weight average molecular weight (Mw) in terms of polystyrene measured by GPC is usually in the range of 1000 or more and 100,000 or less. If the molecular weight of the block copolymer is too small, the dispersion stability decreases, and if it is too large, the developability and resolution tend to decrease.

 [0069] In the present invention, a commercially available acrylic block copolymer having the same structure as that described above can also be applied.

 [0070] [1-2-2] (b) A polymer obtained by polymerizing a monomer component essentially containing a specific compound

 (b) A polymer obtained by polymerizing a monomer component essentially comprising a specific compound as a component is a monomer component essentially comprising a compound represented by the following general formula (1) and / or (2) Refers to a polymer formed by superimposing.

 [Chemical 17]

(In formula (1), R ^la and IT each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)

[Chemical 18]

(In the formula (2), R ^b represents a hydrogen atom or an alkyl group which may have a substituent, L ³ represents a divalent linking group or a direct bond, and X represents the following formula (3): Or an adamantyl group which may be substituted.)

[Chemical 19]

L²及び L³の 2以上が互いに結合 し、環を形成していてもよい。 ) (In the formula (3), R ^z R ^db and R ^4b represent a hydrogen atom, a hydroxyl group, a halogen atom, an amino group, or an organic group, L ¹ and L ² represent a divalent linking group,

Two or more of L ² and L ³ may be bonded to each other to form a ring. )

 Hereinafter, the polymer (b) will be described.

[1-2-2-1] The compound of the general formula (1)

In the general formula (1) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ^la and R ^2a is not particularly limited. ,example For example, linear or branched aralkyl groups such as methylol, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl An alicyclic group such as cyclohexyl, t-butylcyclohexyl, dicyclopentagenyl, tricyclodecanyl, isobornyl, adamantyl, 2-methanolyl 2-adamantyl, etc .; an alkoxy such as 1-methoxyethyl, 1_ethoxyethyl A substituted alkyl group; an alkyl group substituted with an aryl group such as benzyl; and the like. Of these, primary or secondary carbon substituents such as methinole, ethyl, cyclohexyl, and benzyl that are difficult to be removed by heat or heat are preferred in terms of heat resistance. R ^la and R ^2a may be the same type of substituent or different substituents. Specific examples of the ether dimer include, for example, dimethyl _2, 2 ′ — [oxybis (methylene)] bis-2-probenoate, jetyl_2,2 ′ — [oxybis (methylene)] bis-2-pro Penoate, di (n-propyl) -1,2 '— [Oxybis (methylene)] bis—2-Probenoate, di (isopropyl) 2, 2' — [Oxybis (methylene)] bis-2-probe Noate, di ( _n —butyl) 2, 2 '— [oxybis (methylene)] bis 2-propenoate, di (isobutyl) 2, 2' — [oxybis (methylene)] bis 2—probenoate, Di (t butyl) 2, 2 '— [Oxybis (methylene)] bis-2-probenoate, di (tamyl) -2,2' — [Oxybis (methylene)] bis-2—probenoate, di (stear) Ril) 2, 2 '— [Oxybis (methylene)] bis-2-probeno , Di (lauryl) 1 2,2 '— [Oxybis (methylene)] bis-2-probenoate, di (2-ethylhexyl) -2,2' — [oxybis (methylene)] bis-2-pro Benoate, di (1-methoxyethyl) -2,2 '— [Oxybis (methylene)] bis-2-probenoate, di (1-etoxychechinore) _ 2, 2' — [Oxibis (methylene)] bis-2-pro Penoate, dibenzyl-1,2,2 '-[Oxoxybis (methylene)] bis_2-probenoate, diphenyl-1,2,2'-[oxybis (methylene)] bis_2-probenoate, dicyclohexyl 1, 2 '— [Oxybis (methylene)] bis _ 2-Probenoate, di (t-butylcyclohexyl) -1,2,2'-[Oxibis (methylene)] bis-2-probenoate, di (Dicyclopentageninole) 1, 2, 2 '— [Oxibis (methyle )] Bis _ 2—probenoate, di (tricyclodecaninole)-2, 2 '— [oxybis (methylene)] bis _ 2—probenoate, di (isobornyl) 1, 2, 2'- [Oxibis (methylene)] bis 2-probenoate, diadamantyl 2, 2 '[Oxibis (methylene)] bis 2-propenoate, di (2-methyl-2-adamantyl) 2, 2' — [Oxybis ( Methylene)] bis-2-propenoate. Among these, in particular, dimethyl _ 2, 2 '— [oxybis (methylene)] bis _ 2-probenoate, dimethyl 1, 2' — [oxybis (methylene)] bis 1_propenoate, dicyclo Hexanolate 2, 2 '— [Oxybis (methylene)] bis-2-propenoate, dibenzyl-1,2,2' — [Oxybis (methylene)] bis_2-probenoate are preferred. These ether dimers may be only one type or two or more types.

 The polymer (b) can be easily obtained by at least the ether dimer and by polymerizing the monomer components described below. At this time, the cyclization reaction of the ether monomer proceeds simultaneously with the polymerization to form a tetrahydrofuran ring structure.

[0073] The ratio of the ether dimer in the monomer component in obtaining the polymer (b) is not particularly limited, but is 2 to 60% by weight, preferably 5 to 55% in the total monomer component. % By weight, more preferably 5-50% by weight. If the amount of the ether dimer is too large, it may be difficult to obtain a low molecular weight polymer or may be easily gelled. On the other hand, if the amount is too small, the transparency and heat resistance may be reduced. The film performance may be unsatisfactory.

[0074] [1 2-2-2] Regarding the compounds of the general formulas (2) and (3)

In the general formula (2), R ^lb is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.

In the general formula (2), the organic groups represented by R ^2b , R ^3b and R ^4b are, for example, an alkyl group, a cycloalkynole group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an acyl group, a carboxyl group, And an acylenooxy group, preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a cycloalkenyl group having 3 to 18 carbon atoms. An alkoxy group having 1 to 15 carbon atoms, an alkynolethio group having 1 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon atom, and an acyl group having 1 to 15 carbon atoms, and Preferred are an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms. Preferred substituents among R ^z R ′ R ^4b are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.

ΐΛ L ² is not particularly limited as long as it is a divalent linking group, L ³ is a divalent linking group or a direct bond, but at least either L ¹ or L ² is a linking group having 1 or more carbon atoms. It is also preferred that ~ ³ are each independently a direct bond, alkylene having 1 to 15 carbon atoms, --Ο-, --S-, 10 (= 〇) one, 1 to 15 carbon atoms. Alkenylene, phenylene, or a combination thereof is preferred.

As a preferred combination of I ^ to L ³ , L ³ is a direct bond, an alkylene having 1 to 5 carbon atoms, a ring formed by combining with R ^b or R ^4b, and ΐλ L ² has 1 to 5 carbon atoms. Alkylene. Further, as a preferred example of the general formula (3), a compound represented by the following general formula (4) can be cited.

[Chemical 20]

L²と同義であり(In Equation (4), R ^2b , R ^3b , R ^4b , ΐΛ L ² are R ^2b in Equation (3),

Synonymous with L ²

R ^5b and R ^6b represent a hydrogen atom, a hydroxyl group, a halogen atom, an amino group, or an organic group. )

In the general formula (4), the organic groups represented by R ^5b and R ^6b are, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an asinole group, a carboxyl group, an asinoleoxy group, and the like. Preferably, it is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, or a carbon number of 1 to 15 alkoxy groups, alkylthio groups having 1 to 15 carbon atoms, A C1-C15 acyl group, a C1-carboxyl group, and a C1-C15 acyl group, more preferably a C1-C10 alkyl group, C3-C15. This is a cycloalkyl group.

Preferred substituents among R ^{5b and} R ^6b are a hydrogen atom, a hydroxyl group, and an alkynole group having from 10 to 10 carbon atoms.

R ^lb alkyl group, R ^2b R ^4b organic group, L ¹ to: L ³ divalent linking group, and X adamantyl group each independently have a substituent. In particular, it is possible to list the following substituents.

Halogen atom; hydroxyl group; nitro group; cyano group; methyl group, ethyl group, n_propyl group, isopropyl group, n_butyl group, isobutyl group, t_butyl group, amyl group, t_amyl group, n xyl group , N_heptyl group, n-octyl group, t-octyl group, etc., straight or branched alkyl group having 1 18 carbon atoms; carbon such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, etc. Number 3 to: 18 cycloalkyl group; carbon number such as vinyl group, propenyl group, hexenyl group, etc. 2 to: 18 straight chain or branched alkenyl group; carbon such as cyclopentenyl group, cyclohexenyl group, etc. Number 3 18 cycloalkenyl group; methoxy group, ethoxy group, n propoxy group, isopropoxy group, n butoxy group, s-butoxy group, t-butoxy group, ami / reoxy group, tamyloxy group , N hexyloxy group, n ptyloxy group, n-octyloxy group, t-octyloxy group, etc .: 18 linear or branched alkoxy group; methylthio group, ethylthio group, n propinoretio group, isopropylthio group, n —Butylthio, sbutylthio, t-butylthio, amylthio, tamylthio, n xylthio, n butylthio, n-octylthio, t-octylthio, etc. Alkylthio group; phenyl group, tolyl group, xylyl group, mesityl group, etc., C 6 18 aryl group; benzyl group, phenethyl group, etc., C 7-: 18 aralkyl group; buroxy group, propenyloxy A straight chain or branched alkenyloxy group having 2 to 18 carbon atoms such as a hexenyloxy group, a vinylthio group, a propenylthio group, Linear or branched alkenylthio group having a carbon number of 2 18 such as Seniruchio group; - Ashiru group represented by C_〇_R ^17; Ashinoreokishi group represented by one 〇_COR ^18; Cal Bokishiru group _NR ¹⁹ R ² ° An amino group represented by: An asilamino group represented by NHCOR; a carbamate group represented by NHCOOR; a force rubermoyl group represented by CONR ²³ R ²⁴ ; a carboxylic ester group represented by COOR ²⁵ ; a SO NR ²⁶ R ²⁷ Sulfamoyl group; sulfonic acid represented by SO R ²⁸

 3 3

Steryl group; saturated or unsaturated heterocycles such as 2_chenyl group, 2-pyridinole group, furyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, mono-reforino group, pyrrolidinyl group, tetrahydrothiophene dioxide group Groups, trialkylsilyl groups such as trimethylsilyl groups.

R ^{17 to} R ²⁸ are each a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, Or, it has a substituent and represents a aralkyl group.

 Further, the positional relationship of the above substituents is not particularly limited, and when having a plurality of substituents, they may be the same or different.

 Specific examples of the compound represented by the general formula (2) include the following.

[Chemical 21]

21-Ι Ι

IL-ΙΛΙ

01-Ι Ι —

6-Ι Ι ε-ΐΛΐ

8-ΙΛΙ

 -Ι Ι ΙΛΙ

οε 0 S0 / 900Z OAV [Chemical 22]

 M— 16 M -21

本発明に係る前記ポリマー（b)を得る際の単量体成分中における前記一般式（2) の割合は、特に制限されないが、全単量体成分中 0. 5〜60重量％、好ましくは 1〜 55重量％、さらに好ましくは 5〜50重量％であるのがよい。多すぎると、分散剤として 使用する場合、分散体の分散安定性が低下したりするおそれがあり、一方、少なす ぎると、地汚れ適性が低下するおそれがある。

The ratio of the general formula (2) in the monomer component in obtaining the polymer (b) according to the present invention is not particularly limited, but is 0.5 to 60% by weight in the total monomer component, preferably 1 to 55% by weight, more preferably 5 to 50% by weight. If the amount is too large, the dispersion stability of the dispersion may be lowered when used as a dispersant. If it is too close, the soiling suitability may be reduced.

 [0078] [1 2— 2-3] (b) Polymer

 The polymer (b) is preferably a polymer having an acid group. As a result, the resulting curable resin composition has a curable resin composition capable of a cross-linking reaction (hereinafter abbreviated as acid-epoxy curing) utilizing the reaction between an acid group and an epoxy group to form an ester bond. It is possible to make a product or a composition in which an uncured part can be visualized with an alkaline developer. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic acid anhydride group. These acid groups may be used alone or in combination of two or more.

 [0079] In order to introduce an acid group into the polymer, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter referred to as "monomer for introducing an acid group"). May be polymerized as a monomer component. In addition, when an acid group is introduced using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.

 [0080] Examples of the monomer having an acid group include monomers having a powerful carboxy group such as (meth) acrylic acid tataconic acid, monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, maleic anhydride, and anhydride. Power that includes monomers having a carboxylic anhydride group such as itaconic acid Among these, (meth) acrylic acid is particularly preferred. Examples of the monomer capable of imparting an acid group after the polymerization include, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, And monomers having an isocyanate group such as isocyanatoethyl (meth) acrylate. These monomers for introducing an acid group may be only one kind or two or more kinds.

 [0081] When the monomer component for obtaining the polymer also includes a monomer for introducing the acid group, the content ratio is not particularly limited, but is 5 to 70 wt% in the total monomer components. %, Preferably 10 to 60% by weight.

 The polymer may be a polymer having a radical polymerizable double bond.

[0082] In order to introduce a radical polymerizable double bond into the polymer, for example, after polymerization, A monomer capable of imparting a polymerizable double bond (hereinafter also referred to as a “monomer for introducing a radical polymerizable double bond”) is polymerized as a monomer component and will be described later. What is necessary is just to perform the process for providing such a radically polymerizable double bond.

 Examples of the monomer capable of imparting a radical polymerizable double bond after the polymerization include, for example, a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid; and a carboxylic acid anhydride such as maleic anhydride and anhydrous itaconic acid Group-containing monomer; glycidyl (meth) acrylate

3, 4_epoxycyclohexylmethyl (meth) acrylate, monomers having an epoxy group such as 0- (or m-, or p-) benzylbenzyl glycidyl ether, and the like. The monomer for introducing these radical polymerizable double bonds may be only one kind or two or more kinds.

[0083] When the monomer component in obtaining the polymer also includes a monomer for introducing the radical polymerizable double bond, the content ratio is not particularly limited, but the total monomer component during 5-70 _^0/0, and it is preferably 10 to 60 weight ^_0/0.

 In the case of using the compound of the general formula (1) as an essential monomer component, the polymer (b) is preferably a polymer having an epoxy group.

 In order to introduce an epoxy group into the polymer (b), for example, a monomer having an epoxy group (hereinafter sometimes referred to as “monomer for introducing an epoxy group”) is used as a monomer component. What is necessary is just to superpose | polymerize.

 [0084] Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 0- (or m-, or p-) bierpenzinoreguri. Shijinole ether and the like. These monomers for introducing an epoxy group may be only one type or two or more types.

 When the monomer component for obtaining the polymer (b) also includes a monomer for introducing the epoxy group, the content ratio is not particularly limited, but it is 5 to 70 times in all the monomer components. % By weight, preferably 10-60% by weight.

 [0085] The monomer component for obtaining the polymer may contain other copolymerizable monomers, if necessary, in addition to the essential component compounds and monomers.

Examples of the other copolymerizable monomers include, for example, methyl (meth) acrylate, (meth) Ethyl acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as methyl 2-ethylhexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid benzyl, (meth) acrylic acid 2-hydroxyethyl, etc .; styrene, butyltoluene, Aromatic butyl compounds such as methyl styrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadiene or substituted butadiene compounds such as butadiene and isoprene; ethylene, propylene, and salted butyl. Ethylene such as acrylonitrile or substituted ethylene compounds; And the like. Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance. In particular, when used as a dispersant, these other copolymerizable monomers may be used alone or in combination of two or more.

 In particular, when the polymer (b) is used as a dispersant, it is preferable to use (meth) acrylic acid benzenole. In that case, in all monomer components:! To 70% by weight, preferably 5 It should be ~ 60% by weight.

 [0086] When the monomer component for obtaining the polymer also includes the other copolymerizable monomer, the content ratio is not particularly limited, but 95% by weight or less is preferable, and 85% by weight or less. It is more preferable that

 [0087] The polymerization reaction method of the monomer component is not particularly limited, and various conventionally known polymerization methods can be employed, but a solution polymerization method is particularly preferable. The polymerization temperature and polymerization concentration (polymerization concentration = [total weight of monomer components / (total weight of monomer components + solvent weight)] X 100) are determined depending on the type of monomer component used and Ratio, force that varies depending on the target polymer molecular weight Preferably, the polymerization temperature is 40 to 150 ° C, the polymerization concentration is 5 to 50%, and more preferably, the polymerization temperature is 60 to 130 ° C, the polymerization concentration It should be 10-40%.

[0088] When a solvent is used in the polymerization, a solvent used in a normal radical polymerization reaction may be used as the solvent. Specifically, for example, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether Ethers such as ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; methanol Alcohols such as ethanol, isopropanol, n-butanol, ethylene glycol monomethino ethenore, propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; Dimethyl sulfoxide; and the like. These solvents may be used alone or in combination of two or more.

[0089] When the monomer component is polymerized, a commonly used polymerization initiator may be added, if necessary. The polymerization initiator is not particularly limited, but examples thereof include cumene hydroxide, diisopropylbenzene hydride peroxide, di_t_butyl peroxide, lauroyl peroxide, benzoyl peroxide, t_butyl peroxide isopropyl carbonate, t- Organic peroxides such as amylperoxy _ 2 _ethylhexanoate, t-butylperoxy 2-ethylhexanoate; 2, 2'-azobis (isobutyronitrile), 1, 1'-azobis (cyclohexanecarbonitryl), 2 , 2′-azobis (2,4 dimethylvaleronitrile), dimethyl 2,2′-azobis (2 methylpropionate) and the like. These polymerization initiators may be used alone or in combination of two or more. The amount of initiator used is not particularly limited as long as it is appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., but the weight average molecular weight without gelation. Is from 0.1 to 15% by weight, more preferably from 0.5 to 10% by weight, based on the total monomer components.

[0090] When the monomer component is polymerized, a chain transfer agent that is usually used may be added as necessary to adjust the molecular weight. Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercabtan, mercaptoacetic acid and methyl mercaptoacetate, and methylstyrene dimer. Preferably, a residual monomer having a high chain transfer effect is used. N-dodecyl mercaptan and mercaptoacetic acid can be reduced and are easily available. When a chain transfer agent is used, the amount used is particularly limited as long as it is appropriately set according to the combination of monomers used, reaction conditions, target polymer molecular weight, and the like. However, it is possible to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands without gelation. 5 to 10% by weight is preferable.

 [0091] In the case of using the compound of the general formula (1) as an essential monomer component, it is considered that the cyclization reaction of the ether dimer proceeds simultaneously in the polymerization reaction. The cyclization rate of the ether dimer need not necessarily be 100 mol%. When the polymer (b) is obtained, the above-described monomer capable of imparting an acid group is used as a monomer component, and thus when an acid group is introduced, a treatment for imparting an acid group after polymerization is performed. It is necessary to do. The treatment for imparting acid groups varies depending on the type of monomer capable of imparting acid groups. For example, when a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is used. For example, a monomer having an epoxy group such as glycidyl (meth) acrylate may be used if an acid anhydride such as succinic anhydride, tetrahydrophthalenolic anhydride, maleic anhydride or the like is added. In some cases, for example, a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol is added, or an acid such as (meth) acrylic acid is added. For example, an acid anhydride such as succinic acid anhydride, tetrahydrophthalic acid anhydride, maleic acid anhydride may be added to the hydroxyl group generated after In the case of using a monomer having an isocyanate group such as 2-isocyanatoetyl (meth) atalylate, for example, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.

[0092] When the polymer (b) is obtained, a monomer capable of imparting the above-described radical polymerizable double bond is used as the monomer component, thereby introducing a radical polymerizable double bond, It is necessary to perform a treatment for imparting a radical polymerizable double bond later. The treatment for imparting a radically polymerizable double bond varies depending on the type of monomer capable of imparting a radically polymerizable double bond to be used. For example, a monomer having a carboxyl group such as (meth) acrylic acid tataconic acid Glycidyl (meth) acrylate, 3, 4_epoxycyclohexylmethyl (meth) acrylate, 0-(or m-, or p_) burbe Monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride, to which a compound having an epoxy group and a radically polymerizable double bond such as ndinoreglicidinole ether is added. In the case of using glycidyl (meth) acrylate, it is sufficient to add a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate. 4_Epoxycyclohexylmethyl (meth) acrylate, o_ (or m-, or p_) When a monomer having an epoxy group such as benzylbenzyl glycidyl ether is used, an acid such as (meth) acrylic acid is used. If a compound having a group and a radically polymerizable double bond is added,

 [0093] The weight average molecular weight of the polymer (b) is not particularly limited, but is preferably 2000 to 20000, more preferably <5000 to 100,000. When the weight average molecular weight force exceeds S200000, the viscosity becomes too high to form a coating film, and when it is less than 2000, sufficient heat resistance tends to be hardly exhibited.

 When the polymer (b) has an acid group, the acid value is preferably 30 to 500 mgKOH / g, more preferably 50 to 400 mgKOH / g. When the acid value of the polymer (b) is less than 30 mgKH / g, it becomes difficult to apply to alkali development, and when it exceeds 500 mgKOH / g, the viscosity tends to be too high to form a coating film.

 [0094] Incidentally, the polymer obtained by polymerizing the monomer component essentially comprising the compound represented by the general formula (1) of the component (b) is a compound known per se, for example, JP-A-2004-300203. And the compounds described in JP-A-2004-300204.

In addition, component (b) is added to, or instead of, a polymer obtained by polymerizing a monomer component essentially comprising the compound represented by the general formula (1) and / or (2) [2-1] described later in "(W): an epoxy group-containing (meth) Atari rate 5 to 90 mole _{^{0/0, (X):}} (W) other radical polymerizable be copolymerizable with the component compounds 10 to 95 mol% Is produced when (Y) unsaturated monobasic acid is added to 10 to 100 mol% of the epoxy group contained in the copolymer and the above (Y) component is added. It is also possible to use a resin obtained by adding (Z) a polybasic acid anhydride to 10 to 100 mol% of the hydroxyl group.

 [0095] [1 2-3] Other dispersants

The dispersant used in the colorant dispersion of the present invention is not limited to the above-mentioned dispersant, but other It is good, even if it contains a dispersant.

 [0096] Other dispersants used include, for example, urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene ester dispersants, sorbitan aliphatic ester dispersants. Agents, aliphatic modified polyester dispersants, and the like. Specific examples of such dispersants are trade names such as EF KA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by Big Chemi Co., Ltd.), Disparon (manufactured by Enomoto Kasei Co., Ltd.), SOLSPERSE (general) Rikisha Co., Ltd.), KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), Ajispur (Ajinomoto Co., Ltd.), and the like. These polymer dispersants can be used alone or in combination of two or more.

 [0097] In the colorant dispersion of the present invention, the content ratio of (B) dispersant is usually 95% by weight or less, preferably 65% by weight or less, more preferably 50% by weight, based on (A) the colorant. % Or less. If the content of the dispersant is too small, the dispersion stability deteriorates and problems such as reaggregation and thickening occur. On the other hand, if the amount is too large, the ratio of the pigment is relatively reduced, so the coloring power is low, and the film thickness becomes too thick with respect to the color density. Poor control may occur.

 [0098] (a) The content ratio of the graft polymer and / or acrylic block copolymer containing a nitrogen atom is usually 40% by weight or less, preferably 30% by weight or less, based on (A) the colorant. More preferably, it is 20% by weight or less. (A) If the content of the dispersing agent is too small, the dispersion is unstable, and if too large, the image forming properties such as curability deteriorate.

 (b) The content of the polymer obtained by polymerizing the monomer component essentially comprising the compound represented by the general formula (1) and / or (2) is usually 55% by weight based on the (A) colorant. Hereinafter, it is preferably 35% by weight or less, more preferably 30% by weight or less. (B) When the content of the dispersant is too small, the dispersion is unstable, and when too large, the image forming properties such as curability are lowered.

 [0099] [1-3] (C) Solvent

The colorant dispersion of the present invention is generally prepared by dissolving or dispersing the above-described solid content in the solvent (C). (C) The solvent adjusts the viscosity by dissolving or dispersing (A) the color material, (B) the dispersant, and other components blended as necessary in the color material dispersion of the present invention. Plays the function to perform.

As the solvent, for example, diisopropyl ether, mineral spirit, n-pentane, aminoreethenole, ethinorecaprylate, n-hexane, getinoreethenole, isoprene, ethylisobutylether, butyl stearate, n-octane, Barsol # 2, Apco # 18 Sonovent, Diisobutylene, Amyl acetate, Butyl acetate, Apcocinner, Butyl ether, Diisoptyl ketone, Methylcyclohexene, Methyl nonyl ketone, Polypropyl ether, Dodecane, Socal solvent No. 1 and No 2, Amylformate, Dihexyl ether, Diisopropylketone, Solvesso # 150, (n, sec, t) Butyl acetate, Hexene, Shenole TS 28 Solvent, Butyl chloride, Ethyl amyl ketone, Ethyl benzoate , Ami Luku lide, ethylene glycol jetyl ether, ethyl nonoleformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cetosolvate, methyl isoamyl ketone, Methyl isobutyl ketone, propyl acetate, amyl acetate, amyl formate, bicyclohexyl, diethylene glycol monoethyl acetate methanol acetate, dipentene, methoxymethyl pentanol, methyl amino ketone, methyl isopropyl ketone, propyl propionate, propylene glycol t butyl ether Nore, methinoreethylketone, methinorecerosolve, ethenorecerosonoleb, ethinorecerosolvate, carb , Cyclohexanone, Ethyl acetate, Ethyl lactate, Propylene glycol, Propylene glycol monomethyl ether, Propylene glycol monomethyl etherate acetate, Propylene glycol monomethinoatenoate, Propylene glycol monomethenoatenoate acetate, Dipropylene glycolenomonochinoleateol, dipropylene glycolenomonomethinoatenole, dipropylene glycolenomonomethinoleatenolate, 3-methoxypropionic acid, 3_ethoxypropionic acid, 3_ethoxy Methyl propionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, digram Im, ethylene glycol acetate, ethinorecanorebitonore, butylcarb Tol, ethylene glycol monobutyl ether, propylene glycol tert-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate and the like. These solvents may be used alone or in combination of two or more.

 [0101] The content of the solvent in the entire colorant dispersion of the present invention is not particularly limited, but is usually 99% by weight or less, usually 70% by weight or more, preferably 75% by weight or more, and more preferably. It is preferably 80% by weight or more. If the proportion of the solvent is too large, it is inappropriate to form a color material dispersion because the solid content of the color material, dispersant, etc. is too small. On the other hand, if the proportion of the solvent is too small, the viscosity increases and it is not suitable for coating.

 [0102] [1 1 4] Other ingredients

 Although there is no restriction | limiting in particular as another component mix | blended with the coloring material dispersion liquid of this invention as needed, For example, the following component can be contained.

 [1 4 1] Binder resin

 When the pigment dispersion liquid of the present invention is blended in a colored resin composition described later, the colorant dispersion liquid of the present invention may contain a part of the binder resin described below. By including the dispersion stability when producing the colorant dispersion of the present invention can be improved.

 In this case, the addition amount of the kinder resin is preferably 5 to 100% by weight, more preferably 10 to 80% by weight, based on the color material (A) in the color material dispersion. If the amount of binder resin added is less than 5% by weight, the effect of increasing the dispersion stability is insufficient, and if it exceeds 100% by weight, the colorant density decreases, so that a sufficient color density cannot be obtained.

[0103] [1 1 4 1 2] Dispersing aid

Examples of the dispersion aid include pigment derivatives. Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine And derivatives such as pigments. As substituents of pigment derivatives, sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. are included in the pigment skeleton. Examples thereof include those bonded directly or via an alkyl group, aryl group, heterocyclic group, etc., preferably a sulfonamide group and a quaternary salt thereof, a sulfonic acid group, more preferably a sulfonic acid group. is there. In addition, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions. Specific examples of pigment derivatives include azo acid sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, quinacridone pigment sulfonic acid derivatives, and diketopyrrolopyrrole pigments. And sulfonic acid derivatives of dioxazine pigments.

[0104] The addition amount of the pigment derivative is usually from 0.5 to 20% by weight, preferably from 0.5 to 15% by weight, more preferably from 1 to 20%, based on the total solid content of the colorant dispersion of the present invention. : 10% by weight. If the amount of the pigment derivative added is small, the dispersion stability deteriorates and problems such as re-aggregation and thickening occur. On the other hand, if the amount is too large, the contribution to dispersion stability is saturated, and on the contrary, the color purity may be lowered.

 [0105] [1 5] Method for producing colorant dispersion

 Various methods can be adopted as a method for producing the color material dispersion of the present invention.

 First, a predetermined amount of each of the color material, the solvent, and the dispersant is weighed, and in the dispersion treatment step, the color material is dispersed to obtain a liquid color material dispersion. In this dispersion treatment step, a paint conditioner, a sand grinder, a Bono reminole, a Rono reminole, a stone minole, a jet minole, a homogenizer and the like can be used. Since the color material is atomized by performing this dispersion treatment, the colored resin composition using the color material dispersion of the present invention has improved coating characteristics and improved transmittance of the product color filter substrate. .

[0107] When the color material is subjected to a dispersion treatment, the binder resin, the dispersion aid, or the like may be appropriately used in combination. For example, when performing a dispersion treatment using a sand grinder, it is preferable to use glass beads having a diameter of 0.1 to several millimeters or zircoyu beads. The temperature during the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. The dispersion time varies depending on the composition of the color material dispersion (color material, solvent, dispersant, etc.) and the size of the sand grinder apparatus, and therefore needs to be adjusted as appropriate. [0108] [2] Colored resin composition

 Next, the colored resin composition of the present invention will be described.

 The above-described color material dispersion of the present invention is suitably used as a colored resin composition for the purpose of forming a pixel image of a color filter, among other powers that can be used for various applications. As the coloring resin composition, a binder resin, a monomer, a photopolymerization initiator, and other solid contents may be blended together with the pigment dispersion of the present invention. Hereinafter, each component will be described.

 In the section [2], “total solid content” refers to all components of the colored resin composition of the present invention other than the solvent components described later.

 [0109] [2-1] Binder resin

 Examples of the binder resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, and JP-A-11-174224. Known polymer compounds described in 2000-56118, JP2003-233179, JP2004-224894, JP2004-300203, JP2004-300204, etc. are used. Among them, polymer compounds containing no nitrogen atom are preferred, and resins described in JP-A-2004-300203 and JP-A-2004-300204, and (W): epoxy group-containing ( 5) -90 mol% of (meth) acrylate, (X): Epoxy contained in the copolymer obtained by copolymerizing 10-95 mol% of other radical polymerizable compounds that can be copolymerized with component (W) 10 to 100% by weight of the group: (Y) unsaturated monobasic acid is added, and the water produced when the component (Y) is added. 10 to 1 00 mol% (Z) a photosensitive resin obtained by adding a polybasic acid anhydride groups are preferred. The resin described in the above-mentioned JP-A-2004-300203 and JP-A-2004-300204 is a simple substance essentially comprising the specific compound described in [1 1-2-2 (b) of the present specification. Examples include polymers obtained by polymerizing monomer components.

[0110] In addition, (W): epoxy group-containing (meth) acrylates include, for example, glycidinole (meth) acrylate, 3, 4_epoxybutyl (meth) acrylate, (3, 4_epoxycyclohexyl) ) Methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, etc., among which glycidinole (meth) acrylate is preferred. These (W) ingredients May be used alone or in combination of two or more.

[0111] (W): Copolymerization ratio of epoxy group-containing (meth) acrylate (copolymerization ratio when (W) component and (X) component are copolymerized to produce a copolymer. referred to as "copolymerization ratio".) is, the force is as 5-90 mole _^0/0 described above is preferably 20 to 80 mole _^0/0, and more preferable properly is 30 to 70 mol%. If this ratio is too large, the component (X) may decrease and heat resistance and strength may decrease, and if it is too small, the addition amount of the polymerizable component and the alkali-soluble component is insufficient, which is preferable.

[0112] On the other hand, (X): (W) copolymerization ratio of other radical polymerizable compound capable of copolymerizable with the component, the force is as 10 to 95 mole _^0/0 of the preferably 20 to 80 mole ⁰ / ₀ , more preferably 30 to 70 mol%. If this ratio is too large, the amount of the (W) component is reduced, so that the addition amount of the polymerizable component and the alkali-soluble component is insufficient, and if it is too small, the heat resistance and strength are lowered, which is not preferable.

 [0113] Other radical polymerizable compounds that can be copolymerized with the component (X): (W) include one or two mono (meth) acrylates having a structure represented by the following general formula (5). It is preferable to use more than one species.

 [0114] [Chemical 23]

(In the formula (5), R ^{4e to} R ^ye each represents a hydrogen atom or an alkyl group of! To 3 carbon atoms such as methyl, ethyl, propyl, etc., and R ^1Qe and R ^Ue are each hydrogen. An atom or a force that represents an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group, or may be linked to form a ring R ^{1 <) e} and R ^Ue are linked The ring formed is preferably an aliphatic ring It is preferably saturated or unsaturated, and preferably has 5 to 6 carbon atoms. In the general formula (5), mono (meth) acrylate having a structure represented by the following general formula (6), (7), or (8) is preferable. By introducing these structures into the binder resin, heat resistance and strength can be increased. Of course, these mono (meth) acrylates may be used alone or in admixture of two or more.

 [Chemical 24]

[0117] As the mono (meth) acrylate having the structure represented by the chemical formula (5), a force S capable of using various known materials, particularly those represented by the following chemical formula (9) are preferable. .

[0118] [Chemical 25]

CH ₂ ssC— C 1 0— R ¹³ (9)

 II

 0

(In the formula (9), R ¹² represents a hydrogen atom or a methyl group, R ¹³ represents the above chemical formula (5).) A monomer having the structure of the above chemical formula (5) in the copolymerization monomer (meth) including Yuryou Atari rate is usually 5 to 90 mol _^0/0, preferably 10 to 70 mole _^0/0, more preferably from 15 to 5 0 mol _^0/0. [0120] The radically polymerizable compound other than the above is not particularly limited, but specific examples thereof include:

 Styrene, α-, o-, m-, p alkyl, nitro, cyano, amide, esterole derivatives of styrene;

 Gens such as butadiene, 2,3-dimethylbutadiene, isoprene, black-opened plane; methyl (meth) acrylate, ethyl (meth) acrylate, _n-propyl (meth) acrylate, (meth) acrylic acid-iso _Propyl, (meth) acrylic acid _n-butyl, (meth) acrylic acid _sec-butyl, (meth) acrylic acid-tert-butyl, pentyl (meth) acrylate, neopentyl (meth) acrylate, ( Isoamyl acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, (meth) cyclopentyl acrylate, (meth) ) Acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, (meth) acrylic acid dicyclohexyl, (meth) acrylic acid Isoboronyl laurate, adamantyl (meth) acrylate, allylic (meth) acrylate, propaganol (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, ( Anthraninyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, (meth) acrylic Biranyl acid, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, (meth) acrylic acid 1, 1, 1 trifluoroethyl, (meth) acrylic perfluoroethyl, (meta ) Acrylic acid perfluoro-n-propyl, (meth) acrylic acid perful Oro iso propyl, triphenyl methyl (meth) acrylate, Tamyl (meth) acrylate, (meth) acrylic acid 3- (N, N dimethylamino) propyl, (meth) acrylic acid _ 2-hydroxyethyl, (meth) acrylic Acid _ (meth) acrylic acid esters such as 2-hydroxypropyl;

[0121] (Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylolamide, (meth) acrylic acid N,

(Meth) atalinoleamides such as N-jetylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N —di_iso _propylamide, (meth) acrylic acid anthracenylamide; (Meth) acrylic acid anilide, (meth) acryloyl nitrile, acrolein, vinylol chloride, vinylidene chloride, butyl fluoride, vinylidene fluoride, N bulupyrrolidone, burpi Vinyl compounds such as lysine and bier acetate;

 Unsaturated dicarboxylic acid diesters such as cetyl citrate, cetyl maleate, cetyl fumarate, ethyl itaconate;

 Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide;

 Examples include N- (meth) atalyloylphthalimide.

[0122] In order to impart superior heat resistance and strength, it is effective to use at least one selected from styrene, benzyl (meth) acrylate and monomaleimide as the component (X).

In this case, styrene, benzyl (meth) Atari rate and the copolymerization ratio of one is the preferred instrument more preferably 1 to 70 mol% even without least selected from mono-maleimide is 3 to 50 mol ^_0/0.

 [0123] A known solution polymerization method is applied to the copolymerization reaction between the component (W) and the component (X). The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and organic solvents that are usually used can be used.

 Specific examples thereof include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, butylacetate sorb acetate; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether acetate, carbitol acetate and butinorecarbitol acetate. Acetates; propylene glycol monoalkyl ether acetates;

 Acetates such as dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers;

 Diethylene glycol dialkyl ethers such as methyl carbitol, ethinorecanole bitonole, butyl carbitol;

 Triethylene glycol dialkyl ethers;

 Propylene glyconorezianorequinoleateoles;

 Dipropylene glycol dialkyl ethers;

1, 4_dioxane, ethers such as tetrahydrofuran; Acetone, methyl ethyl ketone, ketones such as cyclohexanone, hydrocarbons such as benzene, toluene, xylene, octane, decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha; methyl lactate , Lactate esters such as ethyl lactate and butyl lactate;

 Examples thereof include dimethylformamide and N_methylpyrrolidone.

[0124] These solvents may be used alone or in combination of two or more. The amount of these solvents to be used is 30 to 1000 parts by weight, preferably 50 to 800 parts by weight, with respect to 100 parts by weight of the resulting copolymer. If the amount of solvent used is outside this range, it will be difficult to control the molecular weight of the copolymer.

 The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst azo compound can be used.

[0125] Organic peroxide catalysts are classified into known ketone peroxides, peroxyketals, hard mouth peroxides, diallyl peroxides, disilver oxides, peroxyesters, and peroxydicarbonates. Can be mentioned.

Specific examples of radical polymerization initiators include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, tert-butylenoperoxybenzoate, tert-hexylperoxybenzoate, t-butyl peroxide 2-ethyl Hexanoate, t-hexylperoxy 2-ethyl hexanoate, 1, 1-bis (t-butylperoxy) 3, 3, 5 trimethylcyclohexane, 2, 5 dimethinoleol 2, 5_bis (t-butylperoxy) hexyl _3, 3_isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicuminorehydro peroxide, acetyl chloride, bis (4_ t-butylcyclohexyl) peroxide dicarbonate, diisopropyl peroxide Kisiji -Bonate, isobutyl peroxide, 3, 3, 5_trimethylhexanoyl peroxide, lauryl peroxide, 1,1_bis (t_butylperoxy) 3,3,5-trimethylcyclohexane, 1,1_bis (T-hexylperoxy) 3, 3, 5-trimethylcyclohexane, azobisisobutyronitrile Nore, azobiscarbonamide and the like, and one or more radical polymerization initiators having an appropriate half-life depending on the polymerization temperature are selected and used.

[0126] The amount of the radical polymerization initiator used is 0.5 to 20 parts by weight, preferably 100 parts by weight of the monomers used in the copolymerization reaction, that is, the total of the (W) component and the (X) component, preferably 1 to: 10 parts by weight.

 The copolymerization reaction can be carried out by dissolving the monomer and radical polymerization initiator used in the copolymerization reaction in a solvent and heating while stirring, and then heating the monomer to which the radical polymerization initiator has been added. Can be dropped in a stirred solvent. Alternatively, the monomer may be added dropwise while the radical polymerization initiator is added to the solvent and the temperature is raised. The reaction conditions can be changed freely according to the target molecular weight.

 [0127] The component (Y) to be added to the epoxy group contained in the copolymer of the component (W) and the component (X) is an unsaturated monobasic acid. As the component (Y), known compounds can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond. Specific examples thereof include alicyclic acid, methacrylic acid, crotonic acid, o Examples thereof include monocarboxylic acids such as —, m—, p-bulubenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano substitution. Of these, acrylic acid and / or methacrylic acid are preferred. These (Υ) components may be used alone or in combination of two or more.

[0128] (Υ) component, (W) component and (X). 10 to epoxy groups contained in the copolymer obtained by copolymerization reaction between components: the force to be added to 100 mol _^0/0 preferably 30: 100 mole _^0/0, properly is to be added to 50 to 100 mol% and more preferred. If the addition ratio of component (ii) is too small, there are concerns about adverse effects due to residual epoxy groups such as stability over time.

 As a method of adding the component (ii) to the copolymer of the component (W) and the component (X), a known method can be employed.

[0129] Known polybasic acid anhydrides to be added to the hydroxyl group produced when component (Υ) is added to the copolymer of component (W) and component (X) (Ζ) Dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride Acid, benzophenone tetracarboxylic anhydride, biphenyl tetracarboxylic anhydride And polybasic acid anhydrides. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferable. As the component (Z), one type may be used alone, or two or more types may be used in combination. By adding such components, the binder resin used in the present invention can be made alkali-soluble.

[0130] (Z) component, 10 to the hydroxyl group that is generated when obtained by adding the component (Y): The to be added to 100 mol%, preferably 20 to 90 Monore _^0/0, more preferably 30 to Ru is added to 80 mole _^0/0. If this addition ratio is too large, the residual film ratio during development may decrease, and if it is too small, the solubility will be insufficient.

 As a method of adding the (Z) component to the hydroxyl group produced when the (Y) component is added to the copolymer of the (W) component and the (X) component, a known method can be adopted. .

 [0131] Further, in the present invention, in order to further improve the photosensitivity, after adding (Z) polybasic acid anhydride, glycidinole (meth) acrylate or polymerizable unsaturated group is added to a part of the generated carboxyl group. (Z) Glycidinole ether compound that does not have a polymerizable unsaturated group in a part of the generated carboxyl group after addition of polybasic acid anhydride. Can be added, or both of them may be added. Specific examples of glycidyl ether compounds having no polymerizable unsaturated group include glycidinoreether compounds having a phenyl group or an alkyl group (manufactured by Nagase Kasei Kogyo Co., Ltd., trade names: Denacol EX-111, Denacol EX — 121, Denacol EX—141, Denacol EX—145, Denacol EX—146, Denaconole EX—171, Denacol EX—192), etc.

 [0132] These resin structures are described in, for example, JP-A-8-297366 and JP-A-2001-89533, and are already known.

 The polystyrene-reduced weight average molecular weight (Mw) of such a binder resin measured by GPC is preferably 3000 to 100,000, and particularly preferably 5000 to 50,000. If the molecular weight is less than 3000, the heat resistance and film strength are inferior, and if it exceeds 100000, the solubility in the developer is insufficient, which is not preferable. The molecular weight distribution (weight average molecular weight (Mw) Z number average molecular weight (Mn)) is preferably 2.0 to 5.0.

[0133] Such binder resin may be used alone or in combination of two or more. Also good.

 Such a binder resin, particularly in combination with a urethane-based dispersant or an acrylic-based dispersant described later, has excellent adhesion to the substrate without leaving undissolved matter on the non-image area on the substrate. The effect that a color pixel of density can be formed is preferable.

 [0134] Such a binder resin is usually contained in the range of 0.1 to 80% by weight, preferably 1 to 60% by weight in the total solid content of the colored resin composition of the present invention. When the content of the binder resin is less than this range, the film becomes brittle and the adhesion to the substrate may be lowered. On the other hand, when the amount is larger than this range, the permeability of the developer into the exposed portion increases, and the surface smoothness and sensitivity of the pixel may deteriorate.

 [0135] [2-2] Photopolymerization initiator system

 The photopolymerization initiator is usually used as a mixture (photopolymerization initiator system) with an accelerator and an additive such as a sensitizing dye added as necessary. The photopolymerization initiator system is a component having a function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.

 [0136] Examples of the photopolymerization initiator constituting the photopolymerization initiator system component include metallocenes containing titanocene compounds described in JP-A Nos. 59-152396 and 61-151197. Compounds, hexaarylbiimidazole derivatives described in JP-A-10-39503, halomethyl-s triazine derivatives, N-aryl α-amino acids such as N-phenylglycine, ァ aryl a amino acid salts, N aryl aamino acids Examples include radical activators such as esters, triaminoalkylphenone compounds, and oxime ester initiators described in JP-A No. 2000-80068.

 [0137] Specific examples of the polymerization initiator that can be used in the present invention are listed below.

 2— (4-Methoxyphenyl) 1 4,6-bis (trichloromethyl) 1 s-triazine, 2— (4-methoxynaphthyl) _4, 6 _bis (trichloromethyl) _ s—triazine, 2 _ (4 _Ethoxy naphthyl) 1,4 _bis (trichloromethyl) _ s-triazine, 2 _ (4-ethoxycarbonylnaphthyl) -4, 6 _bis (trichloromethyl) _ s-triazine derivatives ;

2-trichloromethyl 1-5- (2 ^r -benzofuryl) 1 1, 3, 4-oxadiazol, 2— Trichloromethyl-5- [j3- (2'-benzofuryl) bier] 1, 3, 4 oxaziazol nore, 2 trichloromethyl 5- (1- (6'-benzofuryl) vinyl)] 1, 3, 4 Halomethylated oxadiazole derivatives such as oxaziazole, 2-trichloromethyl-5-furyl 1, 3, 4-oxadiazole;

[0138] 2-(2 ^r — Chlorophenyl) 1 4, 5 — Diphenyl imidazole dimer, 2 _ (2 ′ — Black mouth phenyl) 1 4, 5 _bis (3 ′ — methoxyphenyl) ) Imidazole dimer, 2 _ (2 '-phenoleolophenyl) 1,4,5-diphenylimidazole dimer, 2 _ (2'-methoxyphenol) 1 4,5-diphenylimidazole 2 An imidazole derivative such as a dimer, (monomethoxyphenyl) 1,4,5-diph ヱ diimidazole;

 Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether; 2-methylanthraquinone, 2-ethyl anthraquinone, 2 _t-butyl anthraquinone, 1 _ black anthraquinone, etc. Anthraquinone derivatives;

 [0139] Benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-clobenbenzophenone, 4-bromobenzophenone, 2 Noreboxybenzo Benzophenone derivatives such as phenone;

2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, _α -hydroxy 2-methylphenylpropanone, 1-hydroxy-1-1-methylethyl 1- (ρ-isopropylphenol) ketone, 1-hydroxy 1- (dodecylphenyl) ketone, 2-methyl- (4 '(methylthio) phenyl) —2-morpholino 1-propanone, 1, 1, 1-trichloro Acetophenone derivatives such as methyl mono (ρ butylphenyl) ketone;

 Thioxanthone derivatives such as thixanthone, 2-ethylthioxanthone, 2_isopropylthixanthone, 2-chlorothixanthone, 2,4_dimethylthioxanthone, 2,4_jetylthioxanthone, 2,4-diisopropylthioxanthone;

ρ_Dimethylaminobenzoate, Ρ-jetylaminobenzoate, and other benzoate derivatives; 9-phenyllacridine, 9- (ρ-methoxyphenyl) atridine, etc., and ataridin derivatives; 9, 10-dimethylbenzphene Phenazine derivatives such as gin; [0140] Anthrone derivatives such as benzanthrone;

 Di-cyclopentagenyl-Ti-di-dichloride, Di-cyclopentagenyl-Ti-bis fenenore, Dicyclopentageninolet Ti-bis 2, 3, 4, 5, 6 Pentafunole Orofeninore 1-inore, Di-cyclopentageninore _Ti—Bis-1,2,3,5,6-Tetra-Funoleolofeninore _ 1-Inole, Di-cyclopentageninole-Ti-Bis-1,2,4,6 _Trif Norolerofeni _ 1—Inole, Di-cyclopentageninore _Ti_ 2, 6 _Di-Pinoleo Mouth 2 _ 1-Inole, Di-Cyclopenta-Geinore _Ti_ 2, 4_Di-Finoleolofeni _ 1—Inole, Di-I Methylcyclopentagenyl Ti-bis-1, 2, 3, 4, 5, 6-pentafluoropheny _ 1-inole, di-methylolene cyclopentageninore Ti-bis-1,6 _di-funoleorofeni _ 1 _il, di-cyclopentadi Norre _Ti_ 2, 6 _ di one Furuoro 3 titanocene derivatives such as (Pinore one 1 _ I le) Single-phenylene one 1-I le;

 [0141] 2_methyl _ 1 _ [4_ (methylthio) phenyl] _ 2_morpholinopropane _ 1 _one,

 2-Benzyl 2 dimethylamino 1- (4 morpholinophenyl) monobutanone 1, 2 — Benzyl 2 dimethylamino 1- (4 morpholino phenyl) butane 1-1-one, 4-dimethylaminoethyl benzoe- 4-dimethylaminoisoamylbenzene, 4-dimethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1, 4-dimethylaminobenzoate, 2, 5 -Α-Aminoalkylphenone compounds such as bis (4-jetylaminobenzal) cyclohexanone, 7-jetylamino-1-3- (4-jetylaminobenzoyl) coumarin, 4- (jetylamino) chalcone;

 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (0-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9Η -Force rubazol-3-yl]-, 1- (0-acetyloxime), and other oxime ester compounds.

 [0142] Examples of the accelerator constituting the photopolymerization initiator component include Ν, Ν-dimethylaminobenzoic acid ethyl ester, 等, Ν-dialkylaminobenzoic acid alkyl ester, 2-mercaptobenzothiothiol, 2_ Mercaptobenzo compounds having a heterocyclic ring such as mercaptobenzoxazole and 2-mercaptobenzoimidazole, or aliphatic polyfunctional mercapto compounds can be used.

[0143] These photopolymerization initiators and accelerators may be used alone or in combination of two or more. May be used in combination.

 Specific photopolymerization initiator components include, for example, dialkylacetosulfites described on pages 16 to 26 of “Fine Chemical” (1991, March 1 issue, vol. 20, 4ο · 4). Hexalylbiimidazole, S-trihalomethyltriazine described in JP-A-58-403023, JP-B-45-37377, etc., such as enones, benzoin and thixanthone derivatives Containing an ethylenic saturated double bond capable of addition polymerization having a titanocene and a xanthene dye, an amino group or a urethane group, as described in JP-A-4-221958, JP-A-4-219756, etc. Examples include systems that combine compounds.

 [0144] The blending ratio of the photopolymerization initiator component is usually from 0.:! To 40% by weight, and preferably from 0.5 to 30% by weight, based on the total solid content of the colored resin composition of the present invention. If the blending ratio is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if it is extremely high, the solubility of the unexposed part in the developer may be lowered, leading to poor development. If necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source can be added to the photopolymerization initiator system component for the purpose of increasing the sensitivity. Examples of these sensitizing dyes include xanthene dyes described in JP-A-4 221958 and JP-A-4-219756, and coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335. Kaihei 3 No. 239703, No. 5-289335 No. 3 Coumariny compound, Japanese Patent Laid-Open No. 6-19240, Pyromethene dye, Other Nos. 47-2528, No. 54-155292 JP-B-45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69, JP Examples thereof include dyes having a dialkylaminobenzene skeleton described in JP-A-57-168088, JP-A-5-107761, JP-A-5-1988 and JP-A-4-2888.

Of these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4, 4'-dimethylaminobenzophenone, 4,4'-jetylaminoben zofenone, 2-aminobenzofenone, 4-aminominobenzofoenone, 4,4'-diaminovene. Benzophenes such as zofenone, 3, 3'-daminobenzophenone, 3,4-diaminobenzophenone Enone compounds; ² — (p-dimethylaminophenyl) benzoxazole, 2— (ρ-dimethylaminophenyl) benzoxazole, 2 -— (p-dimethylaminophenyl) benzo [4, 5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5_bis (p-jetylaminophenyl) 1,3,4-oxazole, 2_ (p_ Dimethylaminophenyl) benzothiazole, 2_ (p-Jetylaminophenenole) benzothiazole, 2- (p-Dimethylaminophenol) benzimidazole, 2_ (p-Jetylaminophenyl) benzimidazole, 2,5_bis (p-jetylaminophenyl) 1,3,4 —thiadiazole, (p-dimethylaminophenyl) pyridine, (p-jetylaminophenyl) pyridine, (p-dimethyl) P-dialkylaminophenyl group-containing compounds such as (laminophenyl) quinoline, (p-jetylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-jetylaminophenyl) pyrimidine Etc. Of these, 4,4′-dialkylaminobenzophenone is most preferred. Sensitizing dyes may be used alone or in combination of two or more.

 [0146] The blending ratio of the sensitizing dye in the colored composition for a color filter of the present invention is usually 0 to 20% by weight, preferably 0.:! To 15% by weight, based on the total solid content of the colored resin composition. More preferably, 0.2 to 10% by weight.

 [0147] [2-3] Monomer

 The monomer is not particularly limited as long as it contains a photopolymerizable low molecular weight compound that can be polymerized, but at least an ethylenic double bond that is preferably a polyfunctional monomer having a functional group is preferable. One addition-polymerizable compound (hereinafter referred to as “ethylenic compound”) is more preferred. Moreover, the monomer may have an acid group.

 [0148] An ethylenic compound is an ethylenic compound in which, when the colored composition for a color filter of the present invention is irradiated with actinic rays, it undergoes addition polymerization and cures by the action of a photopolymerization initiator described later. It is a compound having a heavy bond. The “monomer” in the present invention means a concept opposite to a so-called polymer substance, and in addition to “monomer” in a narrow sense, “dimer”, “trimer”, “ It means a concept including "oligomer".

[0149] Examples of the ethylenic compound having an acid group include an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid and a monohydroxy compound, an aliphatic polyhydroxy compound and an unsaturated power. Esters of rubonic acid, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, unsaturated carboxylic acids and polyvalent carboxylic acids, and polyhydric hydroxy compounds such as the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds. Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting an ester obtained by an esterification reaction with a compound, a polyisocyanate compound and a (meth) atalyloyl-containing hydroxy compound.

 [0150] Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, ilotonic acid, maleic acid and the like.

 Examples of the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene gallium ditalylate, triethylene glycol ditalylate, trimethylolpropane tritalylate, trimethylol ethane tritalylate, pentaerythritol diester. Acrylate esters such as attalylate, pentaerythritol retriate, pentaerythritol tetraatalylate, dipentaerythritolole tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaoxalate, glycerol acrylate. It is done. In addition, the acrylic acid part of these acrylates was replaced with a methacrylic acid ester substituted for the methacrylic acid part, an itaconic acid ester substituted for the itaconic acid part, a crotonic acid ester substituted for the crotonic acid part, or a maleic acid part. And maleic acid esters.

 [0151] Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydrated quinone diatalylate, hydrated quinone dimetatalylate, resorcin diatalate, resorcin dimetatalylate, pyrogallol tritalylate, and the like. It is done.

 The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound may not necessarily be a single substance but a mixture. Typical examples include condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol and Examples thereof include glycerin condensates.

[0152] Hexamethylene diisocyanate is an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a hydroxy compound containing a (meth) atallyloyl group. , Aliphatic diisocyanates such as trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate Etc., 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1, 1, 1-triallyloyloxymethyl) propane, 3-hydroxy (1, 1, 1-trimethacrylo) And a reaction product with a (meth) ataryloyl group-containing hydroxy compound such as (iloxymethyl) propane.

 [0153] Other examples of the ethylenic compound used in the present invention include acrylamides such as ethylene bisacrylamide; allylic esters such as diaryl phthalate; vinyl group-containing compounds such as dibule phthalate.

 In the present invention, the monomer is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxynole group as in the case of a mixture as described above, it is possible to use this as it is. The hydroxyl group of the compound may be reacted with a non-aromatic carboxylic anhydride to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, and succinic anhydride. Examples include acid and maleic anhydride.

[0154] In the present invention, the monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is added to an unreacted hydroxy group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group by reacting a product is particularly preferred. In this ester, the aliphatic polyhydroxy compound is pentaerythritol and Z or dipentaerythritol.

 [0155] One of these monomers may be used alone. However, since it is difficult to use a single compound in production, two or more of these monomers may be used in combination. If necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination.

As a preferable acid value of the polyfunctional monomer having an acid group, 0.:! To 40 mg_KOHZg And particularly preferably 5 to 30 mg-KH / g. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties will be lowered, and if it is too high, the production and handling will be difficult, the photopolymerization performance will be lowered, and the curability such as the surface smoothness of the pixels will be inferior. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer are adjusted so as to fall within the above range. It is essential.

 [0156] In the present invention, more preferred polyfunctional monomers having an acid group are dipentaerythritol hexaatalylate, dipentaerythritolorepentatalylate, dipentaerythris commercially available as T 01382 manufactured by Toagosei Co., Ltd. It is a mixture of lithonorepentatalylate containing succinate ester as the main component. A combination of other polyfunctional monomers with this polyfunctional monomer can also be used.

The blending ratio of these polyfunctional monomers is usually 5 to 80% by weight, preferably 10 to 70% by weight, based on the total solid content of the colored resin composition of the present invention. %, Preferably 10 to 100 weight. / ₀ , more preferably 20 to 80% by weight. The blending ratio of the multifunctional monomer is appropriately adjusted according to the type of the coloring material of the coloring composition and the acid value of the multifunctional monomer used.

 [0157] [2-4] Organic carboxylic acid, organic carboxylic anhydride

 The coloring composition for a color filter of the present invention may further contain an organic carboxylic acid and / or an organic carboxylic acid anhydride in addition to the above components.

 [2 4 1] Organic carboxylic acid

Examples of organic carboxylic acids include aliphatic carboxylic acids and / or aromatic carboxylic acids. Specific examples of aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, jetyl acetic acid, enanthic acid, strong prillic acid, glycolic acid, acrylic acid, and methacrylic acid. Monocarboxylic acid, oxalic acid, malonic acid, succinic acid, gnoretalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methinoremalonic acid, ethinoremalonic acid, dimethenoremalonic acid, methinoresuccinic acid, tetramethinosuccinic acid , Cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and other dicarboxylic acids, tripotent valeric acid, aconite And tricarboxylic acids such as acid and camphoronic acid. Specific examples of aromatic carboxylic acids include benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid, phthalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, and melophane. Acid, pyromellitic acid, phenylacetic acid, hydroatropic acid, hydrocacinic acid, mandelic acid, phenylsuccinic acid, atropaic acid, kaynic acid, methyl kainate, benzyl kainate, cinnamylidene acetic acid, tamalic acid, umberlic acid, etc. And a carboxylic acid in which a carboxyl group is directly bonded to the phenyl group, a carboxylic acid in which a carboxyl group is bonded to the phenyl group via a carbon bond, and the like.

 [0158] Among the above organic carboxylic acids, malonic acid, particularly preferred are malonic acid, dartaric acid and glycolic acid, among which monocarboxylic acid and dicarboxylic acid are preferred.

 The molecular weight of the organic carboxylic acid is 1000 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid is too large, the effect of improving soil contamination is insufficient. If the molecular weight is too small, the amount added may be reduced or process contamination may occur due to sublimation or volatilization.

 [0159] [2-4 2] Organic carboxylic acid anhydride

 Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and / or aromatic carboxylic acid anhydrides. Specific examples of aliphatic carboxylic acid anhydrides include acetic anhydride, anhydrous trichlorodiacetic acid, anhydrous anhydride. Trifluoroacetic acid, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, dartaric anhydride, 1,2-cyclohexenedicarboxylic anhydride, n-octadecylsuccinic anhydride, 5 — Aliphatic carboxylic acid anhydrides such as norbornene 2,3 dicarboxylic acid. Specific examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalic anhydride, and the like.

 [0160] Among the organic carboxylic acid anhydrides, maleic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, and citraconic anhydride are more preferable.

The molecular weight of the organic carboxylic acid anhydride is usually 800 or less, preferably 600 or less, more preferably 500 or less, and usually 50 or more. If the amount of the above-mentioned organic carboxylic acid anhydride is too large, the effect of improving soil contamination is insufficient, and if it is too small, the amount added may decrease or process contamination may occur due to sublimation or volatilization. [0161] These organic carboxylic acids and organic carboxylic acid anhydrides may be used singly or in combination of two or more.

 These organic carboxylic acids and organic carboxylic anhydrides are added in an amount of usually 0.01% by weight or more, preferably 0.03% by weight Q / o or more in the total solid content of the colored resin composition of the present invention. More preferably, it is 0.05% by weight or more, usually 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less. If the addition amount is too small, a sufficient addition effect cannot be obtained. If the addition amount is too large, surface smoothness and sensitivity are deteriorated, and undissolved peeling pieces may be generated.

[0162] [2-5] Other solids

 The colored resin composition of the present invention may further contain a solid content other than the above components as necessary. Examples of such components include surfactants, thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protective agents, adhesion improvers, and development improvers.

 [2-5-1] Surfactant

 Various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Nonionic surfactants are unlikely to adversely affect various properties. Is preferably used.

The addition amount of the surfactant is usually 0 with respect to the total solid content of the colored resin composition of the present invention. 001-10 weight _^0/0, preferably 0. 005～ :! weight _^0/0, more preferably 0.01 to 0.5% by weight, most preferably 0.03-0.3% by weight. If the addition amount of the surfactant is less than the above range, the smoothness and uniformity of the coating film cannot be expressed, and if it is large, the smoothness and uniformity of the coating film cannot be expressed, and other characteristics deteriorate. There is a case.

[0163] [2-5-5] Thermal polymerization inhibitor

 As the thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, pyrogallolole, catechol, 2,6_t_butyl_p_cresol, β-naphthol and the like are used. The addition amount of the thermal polymerization inhibitor is preferably in the range of 0 to 3% by weight based on the total solid content of the coloring composition of the present invention.

 [2_ 5_ 3] Plasticizer

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, and triethylene. Glycol dicaprylate, dimethyl dallicol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerol and the like are used. The amount of these plasticizers added is preferably 10% by weight or less based on the total solid content of the colored composition of the present invention.

 [0164] [2— 5— 4] Others

 In addition, a storage stabilizer, a surface protective agent, an adhesion improver, a development improver and the like can be added as necessary. The amount of these components added is preferably 20% by weight or less based on the total solid content of the colored composition of the present invention.

[0165] [2-6] Preparation of coloring composition

 Next, specific examples of the method for preparing the colored resin composition of the present invention will be described.

[0166] The colorant dispersion obtained by the dispersion treatment or the like described in [11-5] is blended with a solvent, a binder resin, a polyfunctional monomer, a photopolymerization initiator system component, and, if necessary. Mix other ingredients to make a uniform dispersion. In each of the dispersion treatment step and the mixing step, fine dust may be mixed, and thus the obtained colored resin composition is preferably filtered with a filter or the like.

[0167] [3] Manufacture of color filters

 Next, a specific example of the color filter manufacturing method of the present invention will be described. A color filter is usually manufactured by forming a black matrix on a transparent substrate and then sequentially forming red, green, and blue pixel images.

 The coloring composition for a color filter of the present invention is used as a coating solution for forming a pixel image at least one of black, red, green, and blue. The black resist is formed on the transparent substrate, and the red, green, and blue color resists are formed on the resin black matrix forming surface formed on the transparent substrate, or using a chromium compound or other light shielding metal material. A pixel image of each color is formed on the metal black matrix forming surface by performing coating, heat drying, image exposure, development, and thermosetting.

[0168] [3-1] Transparent substrate (support)

The transparent substrate of the color filter is not particularly limited as long as it is transparent and has adequate strength. Examples of the material include polyethylene terephthalate. Polyester resins such as polyester resins, polypropylene resins such as polypropylene and polyethylene, sheets of thermoplastic resins such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, poly (meth) acrylic resins, etc. The thermosetting resin sheet or various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.

 [0169] In order to improve surface properties such as adhesion, the transparent substrate and the black matrix forming substrate described later have corona discharge treatment, ozone treatment, silane coupling agent, urethane resin, etc. as necessary. A thin film forming process of various resins may be performed.

 The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.:! To 7 mm. In addition, when a thin film forming process of various resins is performed, the film thickness is usually in the range of 0.01 to 10 zm, preferably 0.05 to 5 x m.

 [0170] [3-2] Black matrix

 The black matrix is formed on a transparent substrate using a light-shielding metal thin film or a photosensitive black composition for black matrix. As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide and chromium nitride, nickel and tungsten alloy, etc. are used, and these may be laminated in a plurality of layers.

 [0171] These metal light-shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape by a positive type photoresist, cerium nitrate, perchloric acid and / or Alternatively, an etchant mixed with nitric acid is used, and other materials are etched using an etchant suitable for the material. Finally, the positive photoresist is stripped with a special stripper to remove the black matrix. Can be formed.

 [0172] In this case, first, a thin film of these metal or metal 'metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, after forming a coating film of the colored composition on the thin film, the coating film is exposed and developed using a photomask having a repetitive pattern such as stripes, mosaics, and triangles to form a resist image. Thereafter, the coating film can be etched to form a black matrix.

[0173] On the other hand, when the black composition for black matrix is used, it contains a black color material. The coloring composition is used to form a black matrix. For example, one or more black color materials such as carbon black, black lead, iron black, aniline black, cyanine black, titanium black, etc., or red or green appropriately selected from inorganic or organic pigments and dyes A black matrix can be formed in the same manner as described below for forming a red, green, and blue pixel image using a coloring composition containing a black color material mixed with blue or the like.

[0174] [3-3] Pixel formation

 [3— 3— 1] Formation of coating film

 After applying a coloring composition containing a color material of one of red, green, and blue on a transparent substrate provided with a black matrix and drying, a photomask is overlaid on the formed coating film. A pixel image is formed by performing image exposure, development, and heat curing or photocuring as necessary through the above, to create a colored layer of the pixel image. By performing this operation for each of the three color compositions of red, green, and blue, it is possible to form a color filter image.

 [0175] The coloring composition for the color filter can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, an ink jet method, or the like. In particular, the die coating method significantly reduces the amount of coating solution used and suppresses the generation of foreign substances that are completely free from the effects of mist adhering to the spin coating method. To preferred.

 [0176] If the thickness of the coating film is too thick, pattern development becomes difficult, and it may be difficult to adjust the gap in the liquid crystal cell forming process. Therefore, the desired color expression may not be possible. The thickness of the coating film is usually preferably in the range of 0.2 to 20 xm, more preferably in the range of 0.5 to 10 xm, and still more preferably in the range of 0.2 to 20 xm. It is in the range of 8-5 xm.

 [0177] [3 3-2] Drying of coating film

The drying of the coating film formed by applying the coloring composition to the transparent substrate is preferably performed by a drying method using a hot plate, IR mono-nano, or a competition oven. Usually, after pre-drying, two-stage drying is performed by heating and drying again. Pre-drying conditions are It can be appropriately selected according to the type of solvent component and the performance of the dryer used.

. The drying time is usually selected in the range of 40 to 80 ° C and 15 seconds to 5 minutes, preferably 50 to 70 ° C, depending on the type of solvent component and the performance of the dryer used. Is selected in the range of 30 seconds to 3 minutes.

 [0178] The temperature condition for reheat drying is 50 to 200 ° C higher than the predrying temperature, and 70 to 160 ° C is particularly preferable, and 70 to 130 ° C is particularly preferable. The drying time is preferably 10 seconds to 10 minutes, and more preferably 15 seconds to 5 minutes, depending on the heating temperature. The higher the drying temperature is, the better the adhesion to the transparent substrate is. However, if the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. The coating film may be dried by a reduced pressure drying method in which the temperature is not increased and drying is performed in a reduced pressure chamber.

 [0179] [3-3-3] Exposure process

 Image exposure is carried out by applying a negative matrix pattern on the dried coating film of the colored composition, and irradiating a UV or visible light source through this mask pattern. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the colored composition film in order to prevent a decrease in sensitivity of the colored composition film due to oxygen.

 [0180] The light source used for image exposure is not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc. Lamp light sources such as fluorescent lamps, and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers. An optical filter can also be used when irradiating light of a specific wavelength.

[0181] [3-3-4] Development process

 Development can be performed after the image exposure using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, Inorganic alkaline compounds such as potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, Mono-di- or triethanolamine, mono-di- or tri-methylamine, mono-one di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, Examples include organic alkaline compounds such as ethyleneimine, ethylenedimine, tetramethylammonium hydroxide (TMAH), and choline. These alkaline compounds may be used singly or in combination of two or more.

 [0182] Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. Anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkyl betaines and amino acids. These may be used alone or in combination of two or more.

 [0183] Examples of the organic solvent include one or more of isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butylcetosolve, phencelesolve, propylene glycol, diaceton alcohol and the like. The organic solvent may be used alone or in combination with an aqueous solution.

 The development processing conditions are not particularly limited. Usually, the development temperature is in the range of 10 to 50 ° C, particularly 15 to 45 ° C, particularly preferably 20 to 40 ° C. The development method is immersion development or spray development. , Brush developing method, ultrasonic developing method and the like.

 [0184] [3 3-5] Thermosetting treatment

 The color filter substrate after development is usually subjected to heat curing treatment or light curing treatment, preferably heat curing treatment.

 As for the thermosetting treatment conditions, the temperature is selected in the range of 100 to 280 ° C, preferably in the range of 150 to 250 ° C, and the time is selected in the range of 5 to 60 minutes.

Through these series of steps, the patterning image formation for one color is completed. Follow this process Next, patterning (black,) red, green, and blue is repeated to form a color filter. Note that the order of the three-color patterning of red, green, and blue is not limited to the order described above.

[0185] [3 3-6] Formation of transparent electrode

 The color filter according to the present invention forms a transparent electrode such as ITO on the image as it is and is used as a part of a component such as a color display or a liquid crystal display device. If necessary, a top coat layer such as polyamide or polyimide can be provided on the image.

 In some applications, such as planar alignment drive (IPS mode), the transparent electrode may not be formed.

[0186] [4] Liquid crystal display device (panel)

 Next, a specific example of a method for manufacturing a liquid crystal display device (panel) according to the third aspect of the present invention will be described.

 The liquid crystal display device of the present invention usually forms an alignment film on the color filter of the present invention, spreads a spacer on the alignment film, and then adheres it to a counter substrate to form a liquid crystal cell. It is manufactured by injecting liquid crystal into the formed liquid crystal cell and connecting it to the counter electrode.

[0187] As the alignment film, a resin film such as polyimide is suitable. The alignment film is usually formed by a gravure printing method and / or a flexographic printing method, and the thickness of the alignment film is usually several tens of nm. The alignment film is cured by heat baking, and then subjected to surface treatment by treatment with a rubbing cloth, which is irradiated with ultraviolet rays, to be processed into a surface state capable of adjusting the tilt of the liquid crystal. A spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer having a size of 2 to 8 zm is generally preferable. A transparent resin film photospacer (PS) is formed on the color filter substrate by photolithography, and this can be used instead of the spacer.

 [0188] As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The bonding gap with the counter substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 to 8 zm. After bonding to the counter substrate, other than the liquid crystal injection port The portion is sealed with a sealing material such as an epoxy resin. The sealing material is cured by irradiation with ultraviolet rays (UV) and / or heating, and the periphery of the liquid crystal cell is sealed.

[0189] The liquid crystal cell whose periphery is sealed is cut into panel units, and then the pressure is reduced in the vacuum chamber. After the liquid crystal inlet is immersed in the liquid crystal, the inside of the chamber leaks. Liquid crystal is injected into the liquid crystal cell. Decompression degree in the liquid crystal cell is usually a ^{1 X 10- 2 ~1 X 1 0-} Pa, preferably ^{1 X 10- 3 ~1 X 10- 6} Pa. Further, it is preferable that the liquid crystal cell is heated at the time of depressurization. The heating temperature is usually 30 to 100 ° C, more preferably 50 to 90 ° C. Heating during decompression is usually in the range of 10 to 60 minutes and then immersed in the liquid crystal. A liquid crystal cell filled with liquid crystal is completed by sealing the liquid crystal injection port with a UV curable resin.

 [0190] There are no particular restrictions on the type of liquid crystal, and conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds are used, and any of lyotropic liquid crystals, thermotropic liquid crystals, and the like may be used. Nematic liquid crystal, smectic liquid crystal, and cholesteric liquid crystal are known as thermo-pick pick liquid crystals.

 Example

 [0191] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, this invention is not limited to description of a following example, unless the summary is exceeded.

[0192] <Example:! -6 and comparative example:! -6>

 [1] (a) Synthesis of graft copolymer or acrylic block copolymer (dispersants A to C) containing nitrogen atoms

 [1-1] Synthesis Example 1: Synthesis of Dispersant A

 50 parts by weight of polyethyleneimine having a molecular weight of about 5000, and 40 parts by weight of poly strength prolatatone with n = 5 were mixed with 300 parts by weight of propylene glycol monomethyl ether acetate and stirred at 150 ° C. for 3 hours in a nitrogen atmosphere. . The weight average molecular weight Mw measured by GPC of the dispersant thus synthesized was about 9000.

[0193] [1 2] Synthesis Example 2: Synthesis of Dispersant B

50 parts by weight of polyethyleneimine having a molecular weight of about 5000, 40 parts by weight of poly = prolatatone with n = 5, and 6 parts by weight of stearic acid were mixed with propylene glycol monomethyl ether acetate. The mixture was mixed with 300 parts by weight of a salt and stirred at 150 ° C. for 3 hours under a nitrogen atmosphere. The weight average molecular weight Mw measured by GPC of the dispersant thus synthesized was about 9300.

[0194] [1 1 3] Synthesis Example 3: Synthesis of Dispersant C

 50 parts by weight of polyethyleneimine having a molecular weight of about 10000, 40 parts by weight of poly = prolatathone with n = 5, and 6 parts by weight of stearic acid are mixed with 450 parts by weight of propylene glycol monomethyl etherate, and 150 ° C. for 3 hours. Stir in a nitrogen atmosphere. The weight average molecular weight Mw measured by GPC of the dispersant thus synthesized was about 19000.

 [0195] [1 1 4] Synthesis Example 4: Synthesis of Dispersant D

 A degassed solution of 0.5 mg of the following compound in butyl acrylate (10 ml) was heated at 80 ° C. for 2 hours and subsequently at 120 ° C. for 0.5 hour. Removal of volatiles gave an oligomer with an average Mn = 11. A degassed solution of 200 mg of this oligomer and 10 ml of dimethylaminoethyl methacrylate was heated at 120 ° C. for 1 hour. The colorless gum-like substance which could remove volatile matter was a block copolymer of Mn = 8100, amine value 86 mg-KH / g.

 [0196] [Chemical 26]

[0197] [2] (b) —Synthesis of a polymer (dispersant G, H) obtained by polymerizing a monomer component essentially comprising the compound represented by the general formula (1)

 [2-1] Synthesis example 5: Synthesis of dispersant G

 Prepare a separable flask with a cooling tube as a reaction tank, charge 400 parts by weight of propylene glycol monomethyl ether acetate, purge with nitrogen, and heat in an oil bath with stirring to raise the temperature of the reaction tank to 90 ° C. The temperature was raised to.

[0198] On the other hand, dimethyl-1,2,1, [oxybis (methylene)] bis_2_propenoate 40 parts by weight, methacrylic acid 32 parts by weight, methyl methacrylate 66 parts by weight, methacrylic acid in the monomer tank 62 parts by weight of benzyl, 2.6 parts by weight of t-butylperoxy-2-ethylhexanoate, 40 parts by weight of propylene glycol monomethyl ether acetate, 5.2 parts by weight of n-dodecyl mercaptan in the chain transfer agent tank, 27 parts by weight of propylene glycol monomethyl ether acetate After the temperature of the reaction vessel was stabilized at 90 ° C, dropping was started from the monomer tank and the chain transfer agent tank to initiate polymerization. While maintaining the temperature at 90 ° C, dropping was performed over 135 minutes each, and 60 minutes after the dropping was completed, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a 30 wt% polymer solution having a weight average molecular weight of 17 000 and an oxidation of 103 mg KOH / g.

[0199] [2-2] Synthesis Example 6: Synthesis of Dispersant H

 A separable flask equipped with a cooling tube was prepared as a reaction tank, while 60 parts of dimethylolene 2,2 '-[oxybis (methylene)] bis-2-propenoate and methacrylate were added as a monomer dropping tank. 60 parts, 80 parts of benzyl methacrylate, t-butyl peroxy -2-ethyl hexanoate (“Perbutyl 0” manufactured by NOF Corporation) and 60 parts of diethylene glycol dimethyl ether are mixed and prepared. As a chain transfer agent dropping tank, 8 parts of n-dodecanethiol and 32 parts of diethylene glycol dimethyl ether were prepared with sufficient stirring and mixing.

 The reaction vessel was charged with 375 parts of diethylene glycol dimethyl ether, purged with nitrogen, and heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C, the monomer dropping vessel and the chain transfer agent dropping vessel force dropping were started. The dropwise addition was performed over 135 minutes each while maintaining the temperature at 90 ° C. 60 minutes after the completion of dropping, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C for 3 hours, a gas introduction tube was attached to the separable flask, and publishing of oxygen Z nitrogen = 5Z95 (vZv) mixed gas was started. Next, the reaction vessel was charged with 56 parts of glycidyl methacrylate, 2, 2, monomethylene bis (4 methyl _6_t_butylphenol) and 0.8 part of triethinoreamine, and reacted at 110 ° C for 9 hours. I let you. Thereafter, 128 parts of diethylene glycol dimethyl ether was added and cooled to room temperature to obtain a polymer solution having a concentration of 30%. The weight average molecular weight of the polymer was 19000, and the acid value was 71 mgKOHZg.

[0200] [3] (b) A polymer obtained by polymerizing a monomer component essentially comprising the compound represented by the general formula (2) Synthesis of dispersants (dispersants I to K)

 [3-1] Synthesis Example 7: Synthesis of Dispersant I

 Propylene glycol monomethyl ether acetate 212. 28 parts, V-59 (Wako Pure Chemical Industries, Ltd., azo polymerization initiator) 9 parts were charged in a reaction vessel and heated to 80 ° C under a nitrogen atmosphere. Methyl ethyl ketone 40 o / o dissolution night of compound represented by the formula (hereinafter referred to as “Compound A”) 46. Benzinoremetatalate 83. 03¾, Methinoremetatalate 31. 45¾, 27.05 parts of methacrylic acid was added dropwise over 2 hours, and the mixture was further stirred for 4 hours to obtain a polymerization reaction solution. The binder resin thus obtained had a GPC polymerization average molecular weight of 15000 in terms of polystyrene, and neutralization titration with soot. The acid value was 107. <Compound Α>

 [0201] [Chemical 27]

[0202] [3-2] Synthesis Example 8: Synthesis of Dispersant J

 Propylene glycol monomethyl ether acetate 220.73 parts, V-59 (Wako Pure Chemical Industries, Ltd., azo polymerization initiator) 10 parts were charged into a reaction vessel, and the temperature was raised to 80 ° C under a nitrogen atmosphere. Methyl ethyl ketone 40% solution 32.13 parts, 57.76 parts of benzenoremethacrylate, 21.88 parts of methinoremethacrylate, 44.21 parts of methacrylolate are added dropwise over 2 hours, and 4 more Stirring was performed for a time to obtain a polymerization reaction solution.

Next, 23.30 parts of glycidinole methacrylate, 2,2, monoethylenebis (4-methyl 6-tert-butylphenol) 0.2 parts, and triethylamine 0.4 parts were charged into the reaction vessel as they were at 110.degree. For 9 hours. Thereafter, 128 parts of diethylene glycol dimethyl ether was added and cooled to room temperature to obtain a polymer solution having a concentration of 40%. The weight average molecular weight of the polymer was 12000, and the acid value was 127 mgKOH / g. [0203] [3-3] Synthesis Example 9: Synthesis of Dispersant K

Propylene glycol monomethyl ether acetate 220.73 parts, V-59 (Wako Pure Chemical Industries, Ltd., azo polymerization initiator) 10 parts were charged in a reaction vessel, heated to 80 ° C under nitrogen atmosphere, Compound of formula (hereinafter referred to as “Compound B”), propylene glycol monomethenoate etherate acetate 40 ^ο / ο melted at night 32.13, benzenoremetatalylate 57.76 sound ^ methyl meta 21.88 parts of talylate and 44.21 parts of methacrylolic acid were added dropwise over 2 hours and further stirred for 4 hours to obtain a polymerization reaction solution.

 Next, 23.30 parts of glycidyl methacrylate, 0.2 part of 2,2′-methylenebis (4-methyl-6_t_butylphenol) and 0.4 part of triethylenoleamine were charged into the reaction vessel as they were. The reaction was carried out at 0 ° C for 9 hours. Thereafter, 128 parts of diethylene glycol dimethyl ether was added and cooled to room temperature to obtain a polymer solution having a concentration of 40%. The weight average molecular weight of the polymer was 13000, and the acid value was 113 mgKOH / g.

 <Compound B>

 [0204] [Chemical 28]

[0205] [4] Synthesis of other dispersants (Dispersants L and M)

 [4-1] Synthesis Example 10: Synthesis of dispersant L

The mixture was stirred while purging 145 parts by weight of propylene glycol monomethyl ether acetate with nitrogen, and the temperature was raised to 80 ° C. Thereto were added dropwise 20 parts by weight of a polymethyl methacrylate macromonomer, 15 parts of 2-hydroxyethyl methacrylate, 10 parts of benzyl methacrylate and 35 parts of methacrylic acid, and the mixture was further stirred for 2 hours. Next, propylene glycol monomethyl ether Add 155 parts by weight of ruacetate, add 0.2 parts by weight of p-methoxyphenol and 1.5 parts by weight of triphenylphosphine, dissolve, and then add (3,4-epoxycyclohexyl) methyl tartrate 31 parts by weight A portion of the mixture was added dropwise and reacted at 85 ° C. for 24 hours to obtain a dispersion resin solution having an ethylenically unsaturated group in the side chain. The weight average molecular weight Mw measured by GPC of the thus obtained dispersion resin was about 14000.

[0206] [4-2] Synthesis Example 11: Synthesis of Dispersant M

 Propylene glycol monomethyl ether acetate 35 parts, 1-methoxy_2_propanol 8.8 parts, V-59 (Wako Pure Chemical Industries, Ltd. azo polymerization initiator) 1. Charge 5 parts into a reaction vessel and add nitrogen. In an atmosphere, the temperature was raised to 80 ° C., 9.5 parts of benzyl methacrylate and 6.5 parts of methinoremethalelate 6.5-^-hydroxyethinoremethacrylateate 3.5 咅 ^ methacryloleic acid 10.7 咅 for 2 hours The mixture was added dropwise and further stirred for 4 hours to obtain a polymerization reaction solution. Further, 25.5 parts of propylene glycol monomethyl ether acetate was added to this polymerization reaction solution, 0.05 parts of p_methoxyphenol and 0.3 part of triphenylphosphine were added and dissolved, and then (3, 4 —Epoxycyclohexyl) methyl acrylate 17.5 parts were added dropwise and reacted at 85 ° C. for 24 hours to obtain a resin solution having an ethylenically unsaturated group in the side chain. The binder resin thus obtained had a GPC polymerization average molecular weight of 18000 in terms of polystyrene, and neutralization titration with KOH. The acid value was 50. The rate of introduction to carboxylic acid by (3,4-epoxycyclohexylene) methyl acrylate was 66% from the acid value before and after the reaction.

 [0207] [5] Preparation of pigment dispersion

 [5-1] Examples:! ~ 4, 9 ~: 19, Comparative Examples 1, 3, 4

 CI pigment green 36 as a coloring material 7.20 parts by weight, CI pigment yellow 150 3.09 parts by weight, propylene glycol monomethyl ether acetate as a solvent 60.00 parts by weight, as a dispersant described in Table 1 Dispersant (a) or Dispersant E in total in terms of solid content 1.29 parts by weight, Dispersant (b) or Dispersant L, M listed in Table 1-1, 3.43 parts by weight, diameter 0.5 mm A stainless steel container was filled with 225 parts by weight of Zirco Your beads and dispersed in a paint shaker for 6 hours to prepare a green pigment dispersion.

[0208] [5-2] Examples 5 to 8 and Comparative Examples 2, 5, and 6 CI Pigment Green 36 as a coloring material, 6.00 parts by weight, CI Pigment Yellow 150 as 2.57 parts by weight, propylene glycol monomethyl ether acetate as a solvent, 60.0 parts by weight, and dispersion as described in Table 1 Dispersant (a) or Dispersant F in terms of solid content 2.14 parts by weight, Dispersant (b) or Dispersant L, M listed in Table_1 4.29 parts by weight, diameter 0.5 mm A stainless steel container was filled with 225 parts by weight of Zircoyu beads and dispersed in a paint shaker for 6 hours to prepare a green pigment dispersion.

 [0209] [5-3] Examples 20, 21 and Comparative Example 7

 CI pigment blue 15: 6 as a colorant, 9.47 parts by weight, propylene glycol monomethyl ether acetate as a solvent, 60.00 parts by weight, and dispersant (a) shown in Table 1 as a dispersant 2.37 parts by weight in total, 3.16 parts by weight of Dispersant (b) or Dispersant M listed in Table 1 and 225 parts by weight of Zirconia beads having a diameter of 0.5 mm were filled in a stainless steel container and painted. A blue pigment dispersion was prepared by dispersing for 6 hours in a shaker.

 [0210] [6] Change in viscosity of pigment dispersion

 The viscosity (20 rpm) immediately after production of the pigment dispersion and after standing in a thermostat at 23 ° C. for 7 days was measured using an E-type viscometer “RE-80L” manufactured by Toki Sangyo Co., Ltd. The viscosity of the pigment dispersions in each of the examples and comparative examples was compared with the rate of change in viscosity over 7 days. 1. Those that were 7% or more were ○, 1 · 7% or more and less than 5% △, X from 5% to less than 10%, and XX from 10% or more. The results are shown in Table 1.

[0211] [Table 1]

table 1

"Dispersant E represents a Kusumoto Chemicals, Ltd. polyether amine phosphate salt" DA3 ⁷ 5 J. ²⁾ Preparation of Dispersant F denotes the one company made rDi _spe rbyW61J Bikkukemi. [7] colored resin composition

 Mix other ingredients into the pigment dispersion,

 (i) Implementation column:! ~ 4, 13 ~: 17, 19, Comparison column 1, 3, 4ί or Table 2

(ii) Examples 5 to 8 and Comparative Examples 2, 5, and 6 are shown in Table 3,

(iii) Examples 9 to 12 are shown in Table 4, (iv) Examples 20, 21 and Comparative Example 7 are shown in Table 5,

Each colored resin composition represented was prepared.

 Note that Example 18 was carried out in the same manner as Example 15 except that Dispersant I was used as the binder resin instead of the binder X of Example 15.

[Table 2] Table _2 (Examples 1 to 4, 1 3 to 1 7, 1 9, Comparative Examples 1, 3, 4)

 [Note] * Binder resin X: Compound obtained by adding 3,4-epoxycyclohexylmethyl methacrylate to benzyl methacrylate / methacrylic acid = 7/3 copolymer, Mw = 25,000, oxidation 100mg "KOH / g

[Table 3]

 Table 3 (Examples 5 to 8, Comparative Examples 2, 5, and 6)

[Note] * Pineda resin X: benzyl methacrylate Ζ Methacrylic acid = 7/3 copolymer, 3,4-epoxycyclohexylmethyl methacrylate added, Mw = 25.000, oxidation 100mg "KOH / g [0215] [Table 4]

 Table 1 4 (Examples 9 to 12)

 [Note] ** Binder resin Y: The resin of Synthesis Example 6 (dispersant H) was used as the binder resin.

[0216] [Table 5]

Table 1 5 (Examples 20, 21 and Comparative Example 7)

 [8] Evaluation of re-solubility (measurement of volume average particle diameter mv)

 As an alternative method for evaluating the presence or absence of foreign matter defects in the die coating method, the following re-dissolution and paring was performed.

The colored resin compositions of Examples and Comparative Examples were each applied to a 50 mm square glass substrate by a spin coating method with a dry film thickness of 2.5 zm and air-dried for 60 minutes. Thereafter, it is immersed in 6.25 g of the solvent that forms the colored composition for 3 minutes, redispersed, and after 10 minutes, The particle size distribution was measured with an instrumental Microtrac UPA, and the volume average particle size mv was calculated. A sample having a volume average particle diameter mv of less than 200 nm was designated as ◯, and a particle having a volume average particle size of 200 nm or more was designated as X. The results are shown in Table 1.

 [0218] The occurrence rate of foreign matter defects by the die coating method was 0%, which corresponds to the volume average particle diameter mv in re-dissolvability being 200 nm or less.

 From Table 1-1, the volume average particle size mv was less than 200 nm in the colored resin compositions of the examples. Further, Comparative Examples 1 and 2 were poor in dispersibility and could not be evaluated. From the above results, it was confirmed that the invention of the present application suppresses foreign matter defects caused by die coating.

[0219] [9] Manufacture of color filters

 Each of the colored compositions was spin-coated on a glass substrate on which chromium was deposited, and pre-beta was performed on an 80 ° C. hot plate for 3 minutes. At the time of coating, the rotation speed was adjusted so that the color coordinate y = 0.595 after drying.

 In Examples 20 and 21, and Comparative Example 7, the rotation speed was adjusted so that the color coordinate y = 0.12.

Next, the sample was exposed at 60 mj / cm ² through a mask pattern using a high-pressure mercury lamp, and then developed using a 0.04 wt% aqueous potassium hydroxide solution at a developer temperature of 23 ° C. After the image formation, it was rinsed with sufficient water and then dried with clean air. After that, post-beta was performed in an oven at 230 ° C for 30 minutes. The film thickness after drying was about 1.8 / m.

[0220] [10] Evaluation of surface smoothness of pixels

 The arithmetic average roughness (Ra) of 12.5 μΐη angle was measured for each pixel of the color filter obtained in [9] above using an atomic force microscope SPA300 manufactured by Seiko Denshi Kogyo. The results are shown in Table 1. In addition, Comparative Examples 1 to 4 had poor dispersibility and could not be evaluated.

[0221] [11] Dirt evaluation

The non-image area (on the color filter) of Sampu Nore obtained in [9] was wiped 10 times with a dust-free cloth soaked with 100% ethanol (Toraysee MK Clean Cloth). . The dust-free cloth was fixed to the tip of a lcm x lcm resin square and impregnated with 0. Ice ethanol using a dropper. The pigment adhesion to the dust-free cloth was visually observed, and the presence or absence of the coloring composition in the non-image area after development was evaluated according to the following criteria. as a result Are shown in Table 1.

[0222] ○: Pigment adhesion to a dust-free cloth was not recognized at all.

 (Triangle | delta): The pigment adhesion to a dust-free cloth was recognized very slightly.

 X: Pigment adhesion to a dust-free cloth was clearly observed.

 Table 1 shows that the color filter using the colored resin composition of the example showed no or very little residue by visual observation, whereas Comparative Examples 1 and 2 had poor dispersibility and could not be evaluated. In the color filters using the colored resin compositions of Comparative Examples 5 and 6, visual residue was clearly observed.

[0223] [12] Evaluation of “Kake”

 Observe 20 lines of alternating 50 μm long and 500 μm long lines and spaces from the sample obtained in [9] above. The number of dents (= hangs) that occurred was counted.

 : 20 or less

 ○: 21 or more and 50 or less

 △: 51 or more and 100 or less

 X: 101 or more

 As described above, from Table 1, the colorant dispersion of the present invention has good dispersion stability (no change in viscosity), and the colored resin composition of the present invention has a foreign matter defect suppressing effect, curability, antifouling effect, and It was confirmed that the anti-shrinking effect was also excellent.

[0224] Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention. This application consists of a Japanese patent application filed on November 11, 2004 (Japanese Patent Application 2004-327629) and a Japanese patent application filed on August 30, 2005 (Japanese Patent Application 2005-249271). Which is incorporated by reference in its entirety.

 Industrial applicability

[0225] The present invention has very high industrial applicability in the fields of colorant dispersions, photosensitive coloring compositions, color filters, and liquid crystal display devices for the following reasons (1) to (4). . (1) According to the present invention, a colored resin composition is formed on the non-image area on the substrate when applied on the substrate. It is possible to produce a color filter having a high concentration and a low film thickness that does not deteriorate the image forming ability such as curability, and has excellent adhesion to the substrate with little undissolved material remaining. When applying by die coating, it is possible to provide a colorant dispersion that can suppress dry aggregation at the tip of the die lip and produce a color filter with a high yield.

 (2) According to the present invention, when coated on a substrate, the undissolved colored resin composition is less likely to remain in the non-image area on the substrate. It is possible to produce a color filter with a high density and a low film thickness without reducing the image forming ability, etc., and when applying by die coating, dry aggregation at the tip of the die lip is suppressed, and a color filter is produced with a high yield. The photosensitive coloring composition to be obtained can be provided.

(3) According to the present invention, the non-pixel portion on the substrate has no undissolved photosensitive coloring composition or foreign matter resulting from dry aggregation at the time of die coating application, and has a high concentration and a low film thickness. High quality color filters can be provided.

 (4) According to the present invention, it is possible to provide a high-quality liquid crystal display device using the color filter substrate described in (3).

Claims

Claims (A) Color material, (B) Dispersant and (C) Color material dispersion containing solvent, (B) Graft copolymer containing at least (a) nitrogen atom And / or an acrylic block copolymer, and (b) a polymer obtained by polymerizing a monomer component essentially comprising a compound represented by the following general formula (1) and / or (2) Color material dispersion. [Chemical 1] (In formula (1), R ^la and R ^2a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.) [Chemical 2]

(In the formula (2), R ^lb represents a hydrogen atom or an alkyl group which may have a substituent, L ³ represents a divalent linking group or a direct bond, and X represents the following formula (3): Or an adamantyl group which may be substituted.) [Chemical 3]

(In formula (3), R ^2b , R and R ^4b represent a hydrogen atom, a hydroxyl group, a halogen atom, an amino group, or an organic group, L ¹ and L ² represent a divalent linking group,

Two or more of L ² and L ³ may be bonded to each other to form a ring. ) [2] The color material dispersion according to claim 1, wherein the content of (B) the dispersant is 95% by weight or less based on (A) the color material.  [3] The color according to claim 1 or 2, wherein the content of (a) the graft copolymer and / or acrylic block copolymer containing nitrogen atoms is 40% by weight or less based on (A) the colorant. Material dispersion [4] (b) The content of the polymer obtained by polymerizing the monomer component essentially comprising the compound represented by the general formula (1) and / or (2) is 55% by weight with respect to the (A) colorant. The colorant dispersion according to any one of claims 1 to 3, which is as follows.  [5] A colored resin composition formed using the color material dispersion according to any one of claims 1 to 4.  [6] A colored resin composition containing (A) a colorant, (B) a dispersant, and (C) a solvent, wherein (B) the dispersant contains at least (a) a graft copolymer containing a nitrogen atom, and Z or an acrylic block copolymer, and (b) a polymer obtained by polymerizing a monomer component essentially comprising a compound represented by the following general formula (1) and / or (2) A colored resin composition.  [Chemical 4]

(In formula (1), R ^la and R ^2a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.) [Chemical 5]

(In the formula (2), R ^lb represents a hydrogen atom or an alkyl group which may have a substituent, L ³ represents a divalent linking group or a direct bond, and X represents the following formula (3): Or an adamantyl group which may be substituted.) [Chemical 6] 气 o3b ) L ^{2 (3)} , 0, (In Formula (3), R ^2b , R ^3b , and R ^4b represent a hydrogen atom, a hydroxyl group, a halogen atom, an amino group, or an organic group, L ¹ and L ² represent a divalent linking group,

Two or more of L ² and L ³ may be bonded to each other to form a ring. ) A color formed using the colored resin composition according to claim 5 or 6. A liquid crystal display device formed using the color filter according to claim 7.